Vinyl Terminated Polyethylene with Long Chain Branching

ABSTRACT

Vinyl terminated polyolefins with long chain branching produced with Salan catalysts having carbazole moieties.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. Ser. No.13/921,868, filed Jun. 19, 2013, now U.S. Pat. No. 9,045,568, whichclaims priority to and the benefit of provisional application U.S.61/679,579, filed Aug. 3, 2012, which are hereby incorporated herein byreference.

NAMES OF PARTIES TO JOINT RESEARCH AGREEMENT

(1) ExxonMobil Chemical Company, A Division of ExxonMobil Corporation;and (2) Ramot at Tel Aviv University Ltd.

FIELD OF THE INVENTION

This invention relates to vinyl terminated ethylene polymers and/orpolymers having long chain branching made with novel catalyst compoundscomprising Salan ligands.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hencethere is interest in finding new catalyst systems that increase thecommercial usefulness of the catalyst and allow the production ofpolymers having improved properties.

There is a need in the art for new and improved catalysts and catalystsystems to obtain new and improved polyolefins, polymerizationprocesses, and the like. Accordingly, there is a need in the art for newand improved catalyst systems for the polymerization of olefins, inorder to achieve specific polymer properties, such as high polymermelting point, high polymer molecular weights, long chain branching,vinyl termination, to increase conversion or comonomer incorporation,and/or to alter comonomer distribution without deterioration of theproperties of the resulting polymers.

SUMMARY OF THE INVENTION

The instant disclosure is directed to catalyst compounds, catalystsystems comprising such compounds, processes for the preparation of thecatalyst compounds and systems, and processes for the polymerization ofolefins using such catalyst compounds and systems.

In an embodiment, a process comprises:

-   -   contacting one or more olefins with a catalyst system at a        temperature, a pressure, and for a period of time sufficient to        produce a polyolefin comprising        -   a) at least 50% allyl chain ends; and        -   b) an Mn of at least 200 g/mol, as determined by ¹H NMR;    -   the catalyst system comprising an activator and a catalyst        compound according to Formula I, Formula II, or a combination        thereof:

Formula I being represented by:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl        radical, a    -   functional group comprising elements from Groups 13-17 of the        periodic table of the elements, or X¹ and X² join together to        form a C₄ to C₆₂ cyclic or polycyclic ring structure, provided,        however, where M is trivalent then X² is not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or two or more of        R¹ to R²⁸ may independently join together to form a C₄ to C₆₂        cyclic or polycyclic ring structure, or a combination thereof,        or a combination thereof; and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl;

Formula II being represented by:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or X¹ and X² join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided, however, where M is trivalent then X² is        not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently, a        hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group        comprising elements from Group 13-17 of the periodic table of        the elements, or two or more of R¹ to R²¹ may independently join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, or a combination thereof; subject to the proviso that        R¹⁹ is not a carbazole or a substituted carbazole radical, and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

In an embodiment, a polyolefin polymer comprises:

-   -   a) at least 50% allyl chain ends; and    -   b) an Mn of at least 200 g/mol, as determined by ¹H NMR;    -   the polymer produced by a process comprising:    -   contacting one or more olefins with a catalyst system at a        temperature, a pressure, and for a period of time sufficient to        produce the polyolefin polymer,    -   the catalyst system comprising an activator and a catalyst        compound according to Formula I, Formula II, or a combination        thereof:

Formula I being represented by:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or X¹ and X² join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided, however, where M is trivalent then X² is        not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or two or more of        R¹ to R²⁸ may independently join together to form a C₄ to C₆₂        cyclic or polycyclic ring structure, or a combination thereof,        or a combination thereof; and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl;

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or X¹ and X² join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided, however, where M is trivalent then X² is        not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently, a        hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group        comprising elements from Group 13-17 of the periodic table of        the elements, or two or more of R¹ to R²¹ may independently join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, or a combination thereof; subject to the proviso that        R¹⁹ is not a carbazole or a substituted carbazole radical, and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

DETAILED DESCRIPTION

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as in Chem. Eng.News, 1985, 63, 27. Therefore, a “Group 4 metal” is an element fromGroup 4 of the Periodic Table.

In the structures depicted throughout this specification and the claims,a solid line indicates a bond, an arrow indicates that the bond may bedative, and each dashed line represents a bond having varying degrees ofcovalency and a varying degree of coordination.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document unless otherwisespecified. For purposes of this disclosure, a hydrocarbyl radical isdefined to be C₁ to C₇₀ radicals, or C₁ to C₂₀ radicals, or C₁ to C₁₀radicals, or C₆ to C₇₀ radicals, or C₆ to C₂₀ radicals, or C₇ to C₂₀radicals that may be linear, branched, or cyclic where appropriate(aromatic or non-aromatic); and includes hydrocarbyl radicalssubstituted with other hydrocarbyl radicals and/or one or morefunctional groups comprising elements from Groups 13-17 of the periodictable of the elements. In addition two or more such hydrocarbyl radicalsmay together form a fused ring system, including partially or fullyhydrogenated fused ring systems, which may include heterocyclicradicals.

For purposes herein, a carbazole or substituted carbazole radical isrepresented by the formula:

wherein each R¹ through R⁸ is, independently, a hydrogen, a C₁-C₄₀hydrocarbyl radical, a functional group comprising elements from Group13-17 of the periodic table of the elements, or two or more of R¹ to R⁸may independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure, or a combination thereof.

The term “substituted” means that a hydrogen atom and/or a carbon atomin the base structure has been replaced with a hydrocarbyl radical,and/or a functional group, and/or a heteroatom or a heteroatomcontaining group. Accordingly, the term hydrocarbyl radical includesheteroatom containing groups. For purposes herein, a heteroatom isdefined as any atom other than carbon and hydrogen. For example, methylcyclopentadiene (Cp) is a Cp group, which is the base structure,substituted with a methyl radical, which may also be referred to as amethyl functional group, ethyl alcohol is an ethyl group, which is thebase structure, substituted with an —OH functional group, and pyridineis a phenyl group having a carbon in the base structure of the benzenering substituted with a nitrogen atom.

For purposes herein, a hydrocarbyl radical may be independently selectedfrom substituted or unsubstituted methyl, ethyl, ethenyl and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl,tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl,pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl,triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl,nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl,pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl,eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl,pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, andtriacontynyl.

For purposes herein, hydrocarbyl radicals may also include isomers ofsaturated, partially unsaturated and aromatic cyclic structures whereinthe radical may additionally be subjected to the types of substitutionsdescribed above. The term “aryl”, “aryl radical”, and/or “aryl group”refers to aromatic cyclic structures, which may be substituted withhydrocarbyl radicals and/or functional groups as defined herein.Examples of aryl radicals include: acenaphthenyl, acenaphthylenyl,acridinyl, anthracenyl, benzanthracenyls, benzimidazolyl,benzisoxazolyl, benzofluoranthenyls, benzofuranyl, benzoperylenyls,benzopyrenyls, benzothiazolyl, benzothiophenyls, benzoxazolyl, benzyl,carbazolyl, carbolinyl, chrysenyl, cinnolinyl, coronenyl, cyclohexyl,cyclohexenyl, methylcyclohexyl, dibenzoanthracenyls, fluoranthenyl,fluorenyl, furanyl, imidazolyl, indazolyl, indenopyrenyls, indolyl,indolinyl, isobenzofuranyl, isoindolyl, isoquinolinyl, isoxazolyl,methyl benzyl, methylphenyl, naphthyl, oxazolyl, phenanthrenyl, phenyl,purinyl, pyrazinyl, pyrazolyl, pyrenyl, pyridazinyl, pyridinyl,pyrimidinyl, pyrrolyl, quinazolinyl, quinolonyl, quinoxalinyl,thiazolyl, thiophenyl, and the like.

It is to be understood that for purposes herein, when a radical islisted, it indicates that the base structure of the radical (the radicaltype) and all other radicals formed when that radical is subjected tothe substitutions defined above. Alkyl, alkenyl, and alkynyl radicalslisted include all isomers including where appropriate cyclic isomers,for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl,tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls);pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1-ethylpropyl, and nevopentyl (and analogous substitutedcyclobutyls and cyclopropyls); butenyl includes E and Z forms of1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl (andcyclobutenyls and cyclopropenyls). Cyclic compounds having substitutionsinclude all isomer forms, for example, methylphenyl would includeortho-methylphenyl, meta-methylphenyl and para-methylphenyl;dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and3,5-dimethylphenyl.

Likewise the terms “functional group”, “group” and “substituent” arealso used interchangeably throughout this document unless otherwisespecified. For purposes herein, a functional group includes both organicand inorganic radicals or moieties comprising elements from Groups 13,14, 15, 16, 17 of the periodic table of elements. Suitable functionalgroups may include hydrocarbyl radicals, e.g., alkyl radicals, alkeneradicals, aryl radicals, and/or halogen (Cl, Br, I, F), O, S, Se, Te,NR*_(x), OR*, SeR*, TeR*, PR*_(x), AsR*_(x), SbR*_(x), SR*, BR*_(x),SiR*_(x), GeR*_(x), SnR*_(x), PbR*_(x), and/or the like, wherein R is aC₁ to C₂₀ hydrocarbyl as defined above and wherein x is the appropriateinteger to provide an electron neutral moiety. Other examples offunctional groups include those typically referred to as amines, imides,amides, ethers, alcohols (hydroxides), sulfides, sulfates, phosphides,halides, phosphonates, alkoxides, esters, carboxylates, aldehydes, andthe like.

For purposes herein an “olefin,” alternatively referred to as “alkene,”is a linear, branched, or cyclic compound comprising carbon and hydrogenhaving at least one double bond. For purposes of this specification andthe claims appended thereto, when a polymer or copolymer is referred toas comprising an olefin, the olefin present in such polymer or copolymeris the polymerized form of the olefin. For example, when a copolymer issaid to have an “ethylene” content of 35 wt % to 55 wt %, it isunderstood that the mer unit in the copolymer is derived from ethylenein the polymerization reaction and said derived units are present at 35wt % to 55 wt %, based upon the weight of the copolymer.

For purposes herein a “polymer” has two or more of the same or different“mer” units. A “homopolymer” is a polymer having mer units that are thesame. A “copolymer” is a polymer having two or more mer units that aredifferent from each other. A “terpolymer” is a polymer having three merunits that are different from each other. “Different” in reference tomer units indicates that the mer units differ from each other by atleast one atom or are different isomerically. Accordingly, thedefinition of copolymer, as used herein, includes terpolymers and thelike. An oligomer is typically a polymer having a low molecular weight,such an Mn of less than 25,000 g/mol, or in an embodiment less than2,500 g/mol, or a low number of mer units, such as 75 mer units or less.An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymercomprising at least 50 mole % ethylene derived units, a “propylenepolymer” or “propylene copolymer” is a polymer or copolymer comprisingat least 50 mole % propylene derived units, and so on.

For the purposes of this disclosure, the term “α-olefin” includes C₂-C₂₂olefins. Non-limiting examples of α-olefins include ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene,1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbomane.Non-limiting examples of cyclic olefins and diolefins includecyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbomene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbomadiene, dicyclopentadiene, 5-ethylidene-2-norbomene,vinylcyclohexene, 5-vinyl-2-norbomene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane.

The terms “catalyst”, “catalyst compound”, and “transition metalcompound” are defined to mean a compound capable of initiatingpolymerization catalysis under the appropriate conditions. In thedescription herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, or a transition metal compound, andthese terms are used interchangeably. A catalyst compound may be used byitself to initiate catalysis or may be used in combination with anactivator to initiate catalysis. When the catalyst compound is combinedwith an activator to initiate catalysis, the catalyst compound is oftenreferred to as a pre-catalyst or catalyst precursor.

A “catalyst system” is combination of at least one catalyst compound, atleast one activator, an optional co-activator, and an optional supportmaterial, where the system can polymerize monomers to polymer. For thepurposes of this invention and the claims thereto, when catalyst systemsare described as comprising neutral stable forms of the components it iswell understood by one of ordinary skill in the art that the ionic formof the component is the form that reacts with the monomers to producepolymers.

For purposes herein the term “catalyst productivity” is a measure of howmany grams of polymer (P) are produced using a polymerization catalystcomprising W g of catalyst (cat), over a period of time of T hours; andmay be expressed by the following formula: P/(T×W) and expressed inunits of gPgcat⁻hr⁻. Conversion is the amount of monomer that isconverted to polymer product, and is reported as mol % and is calculatedbased on the polymer yield and the amount of monomer fed into thereactor. Catalyst activity is a measure of how active the catalyst isand is reported as the mass of product polymer (P) produced per mole ofcatalyst (cat) used (kg P/mol cat).

An “anionic ligand” is a negatively charged ligand which donates one ormore pairs of electrons to a metal ion. A “neutral donor ligand” is aneutrally charged ligand which donates one or more pairs of electrons toa metal ion.

A scavenger is a compound that is typically added to facilitateoligomerization or polymerization by scavenging impurities. Somescavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Inan embodiment a co-activator can be pre-mixed with the catalyst compoundto form an alkylated catalyst compound.

A propylene polymer is a polymer having at least 50 mol % of propylene.As used herein, Mn is number average molecular weight as determined byproton nuclear magnetic resonance spectroscopy (¹H NMR) unless statedotherwise, Mw is weight average molecular weight determined by gelpermeation chromatography (GPC), and Mz is z average molecular weightdetermined by GPC, wt % is weight percent, and mol % is mole percent.Molecular weight distribution (MWD) is defined to be Mw divided by Mn.Unless otherwise noted, all molecular weight units, e.g., Mw, Mn, Mz,are g/mol.

The following abbreviations may be used through this specification: Meis methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl,n-Pr is normal propyl, Bu is butyl, iso-butyl is isobutyl, sec-butylrefers to secondary butyl, tert-butyl, refers to tertiary butyl, n-butylis normal butyl, pMe is para-methyl, Bz is benzyl, THF istetrahydrofuran, Mes is mesityl, also known as 1,3,5-trimethylbenzene,Tol is toluene, TMS is trimethylsilyl, TIBAL is triisobutylaluminum,TNOAL is triisobutyl n-octylaluminum, MAO is methylalumoxane, and MOMOis methoxymethoxy (also referred to as methoxymethyl ether).

For purposes herein, RT is room temperature, which is defined as 25° C.unless otherwise specified. All percentages are weight percent (wt %)unless otherwise specified.

In the description herein, the Salan catalyst may be described as acatalyst precursor, a pre-catalyst compound, Salan catalyst compound ora transition metal compound, and these terms are used interchangeably.

Catalyst Compounds

In an embodiment, the catalyst comprises Group 3, 4, 5 and/or 6disubstituted compounds supported by a tetradentate di-anionic Salanligand, useful to polymerize olefins and/or α-olefins to producepolyolefins and/or poly(α-olefins).

In an embodiment, the catalyst compounds are represented by thefollowing structure:

-   -   where each solid line represents a covalent bond and each dashed        line represents a bond having varying degrees of covalency and a        varying degree of coordination;    -   M is a Group 3, 4, 5 or 6 transition metal covalently bonded to        each oxygen atom, and bonded with varying degrees of covalency        and coordination to each of nitrogen atoms N¹ and N²;    -   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or X¹ and X² join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided, however, where M is trivalent then X² is        not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷ and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl,        a functional group comprising elements from Group 13-17 of the        periodic table of the elements, or two or more of R¹ to R²⁸ may        independently join together to form a C₄ to C₆₂ cyclic or        polycyclic ring structure, or a combination thereof; and    -   Y is a divalent hydrocarbyl radical covalently bonded to and        bridging between both of the nitrogen atoms N¹ and N². In an        embodiment, two or more of R¹ to R²⁸ may independently join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure.

In an embodiment, the catalyst compound is represented by the formula:

-   -   wherein A is represented by the formula, attached to the        nitrogen atom, labeled N³ of the carbazole ring:

-   -   wherein A′ is represented by the formula, attached to the        nitrogen atom labeled N⁴ of the carbazole ring:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or X¹ and X² join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided, however, where M is trivalent then X² is        not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl        radical, a functional group comprising elements from Group 13-17        of the periodic table of the elements, or two or more of R¹ to        R²⁸ may independently join together to form a C₄ to C₆₂ cyclic        or polycyclic ring structure, or a combination thereof; and    -   Y and Z form a divalent C₁ to C₂₀ hydrocarbyl radical. In an        embodiment, Y and Z are identical. In an embodiment, Y and Z are        different.

In an embodiment, M is a Group 4 metal, or M is Hf, Ti and/or Zr, or Mis Hf or Zr. In an embodiment, each of X¹ and X² is independentlyselected from the group consisting of hydrocarbyl radicals having from 1to 20 carbon atoms, hydrides, amides, alkoxides having from 1 to 20carbon atoms, sulfides, phosphides, halides, amines, phosphines, ethers,and combinations thereof.

In an embodiment, X¹ and X² together form a part of a fused ring or aring system having from 4 to 62 carbon atoms.

In an embodiment, each of X¹ and X² is independently selected from thegroup consisting of halides, alkyl radicals having from 1 to 7 carbonatoms, benzyl radicals, or a combination thereof.

In an embodiment, Y is a divalent C₁-C₂₀ hydrocarbyl radical comprisinga portion that comprises a linker backbone comprising from 1 to 18carbon atoms linking or bridging between nitrogen atoms N¹ and N². In anembodiment, Y is a C₁-C₂₀ hydrocarbyl radical comprising a portion thatcomprises a linker backbone comprising from 1 to 18 carbon atoms linkingthe nitrogen atoms N¹ and N² wherein the hydrocarbyl comprises O, S,S(O), S(O)₂, Si(R*)₂, P(R*), or N(R*), wherein each R* is independentlya C₁-C₁₈ hydrocarbyl. In an embodiment, Y is selected from the groupconsisting of ethylene (—CH₂CH₂—) and 1,2-cyclohexylene, and/or—CH₂CH₂CH₂— derived from propylene. In an embodiment, Y is—CH₂CH₂CH₂-derived from propylene.

In an embodiment, each X is, independently, a halogen or a C₁ to C₇hydrocarbyl radical.

In an embodiment, each X is a benzyl radical. In an embodiment, each R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is,independently, hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl radical,or a C₁ to C₁₀ hydrocarbyl radical. In an embodiment, one or more of R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is a methylradical, a fluoride, or a combination thereof.

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹ and R¹⁴ aremethyl radicals; R² through R¹³ and R¹⁵ through R²⁸ are hydrogen; and Yis ethylene (—CH₂CH₂—).

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴and R¹⁷ are methyl radicals; R², R³, R⁵ through R¹³, R¹⁵, R¹⁶ and R¹⁸through R²⁸ are hydrogen; and Y is ethylene (—CH₂CH₂—).

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹ and R¹⁴ aremethyl radicals; R⁴ and R¹⁷ are fluoro (F) functional groups; R², R³, R⁵through R¹³, R¹⁵, R¹⁶ and R¹⁸ through R²⁸ are hydrogen; and Y isethylene (—CH₂CH₂—).

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴and R¹⁷ are methyl radicals; R⁸, R¹¹, R²¹ and R²⁴ are tert-butylradicals; R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹,R²⁰, R²², R²³, R²⁵, R²⁶, R²⁷, and R²⁸ are hydrogen; and Y is ethylene(—CH₂CH₂—).

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴and R¹⁷ are methyl radicals; R⁸, R¹¹, R²¹ and R²⁴ are mesityl radicals;R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²²,R²³, R²⁵, R²⁶, R²⁷, and R²⁸ are hydrogen; and Y is ethylene (—CH₂CH₂—).

In an embodiment, the catalyst compounds are represented by thefollowing structure:

-   where each solid line represents a covalent bond and each dashed    line represents a bond having varying degrees of covalency and a    varying degree of coordination;-   M is a Group 3, 4, 5 or 6 transition metal covalently bonded to each    oxygen atom, and bonded with varying degrees of covalency and    coordination to each of nitrogen atoms N¹ and N²;-   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical,    a functional group comprising elements from Groups 13-17 of the    periodic table of the elements, or X¹ and X² join together to form a    C₄ to C₆₂ cyclic or polycyclic ring structure, provided, however,    where M is trivalent then X² is not present;-   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is independently, a hydrogen,    a C₁-C₄₀ hydrocarbyl, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹ to R²¹ may independently join together to form a C₄ to C₆₂ cyclic    or polycyclic ring structure, or a combination thereof, subject to    the proviso that R¹⁹ is not a carbazole or a substituted carbazole    radical; and-   Y is a divalent hydrocarbyl radical covalently bonded to and    bridging between both of the nitrogen atoms N¹ and N². In an    embodiment, two or more of R¹ to R²¹ may independently join together    to form a C₄ to C₆₂ cyclic or polycyclic ring structure.

Accordingly, the instant disclosure in one embodiment is directed tonon-symmetrical Salan catalysts. The Salan catalysts disclosed hereinare devoid of a symmetry element, having a non-symmetric ornon-palindromic structure. By non-symmetric, it is meant that the twophenol moieties of the Salan compound are substituted differently whencomparing the substitutions of one phenol, which comprises a carbazoleor substituted carbazole radical, and the other phenol which does notcomprise a carbazole or a substituted carbazole radical at position R¹⁹(i.e., subject to the proviso that R¹⁹ is not a carbazole or asubstituted carbazole radical), as is shown in the above structure.

In an embodiment, a catalyst compound is represented by the structure

-   wherein A is represented by the structure attached at the carbazole    nitrogen atom:

-   where each solid line represents a covalent bond and each dashed    line represents a bond having varying degrees of covalency and a    varying degree of coordination;-   M is a Group 3, 4, 5 or 6 transition metal covalently bonded to each    oxygen atom, and bonded with varying degrees of covalency and    coordination to each of nitrogen atoms N¹ and N²;-   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical,    a functional group comprising elements from Groups 13-17 of the    periodic table of the elements, or X¹ and X² join together to form a    C₄ to C₆₂ cyclic or polycyclic ring structure, provided, however,    where M is trivalent then X² is not present;-   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is independently, a hydrogen,    a C₁-C₄₀ hydrocarbyl, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,    R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ may independently join together to    form a C₄ to C₆₂ cyclic or polycyclic ring structure, or a    combination thereof, subject to the proviso that R¹⁹ is not    identical to A; and Y and Z form a divalent hydrocarbyl radical    covalently bonded to and bridging between both of the nitrogen atoms    N¹ and N². In an embodiment, Y is identical to Z.

In an embodiment, Y is different to Z. In an embodiment, two or more ofR¹ to R²¹ may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.

In an embodiment, M is a Group 4 metal, or M is Hf, Ti and/or Zr, or Mis Hf or Zr. In an embodiment, each of X¹ and X² is independentlyselected from the group consisting of hydrocarbyl radicals having from 1to 20 carbon atoms, hydrides, amides, alkoxides having from 1 to 20carbon atoms, sulfides, phosphides, halides, amines, phosphines, ethers,and combinations thereof.

In an embodiment, X¹ and X² together form a part of a fused ring or aring system having from 4 to 62 carbon atoms.

In an embodiment, each of X¹ and X² is independently selected from thegroup consisting of halides, alkyl radicals having from 1 to 7 carbonatoms, benzyl radicals, or a combination thereof.

In an embodiment, Y is a divalent C₁-C₄₀ hydrocarbyl radical comprisinga portion that comprises a linker backbone comprising from 1 to 18carbon atoms linking or bridging between nitrogen atoms N¹ and N². In anembodiment, Y is a C₁-C₄₀ hydrocarbyl radical comprising a portion thatcomprises a linker backbone comprising from 1 to 18 carbon atoms linkingthe nitrogen atoms N¹ and N² wherein the hydrocarbyl comprises O, S,S(O), S(O)₂, Si(R*)₂, P(R*), or N(R*), wherein each R* is independentlya C₁-C₁₈ hydrocarbyl. In an embodiment, Y is selected from the groupconsisting of ethylene (—CH₂CH₂—) and 1,2-cyclohexylene, and/or—CH₂CH₂CH₂-derived from propylene. In an embodiment, Y is —CH₂CH₂CH₂—derived from propylene.

In an embodiment, each X is, independently, a halogen or a C₁ to C₇hydrocarbyl radical.

In an embodiment, each X is a benzyl radical. In an embodiment, each R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently, hydrogen, a halogen, or a C₁to C₃₀ hydrocarbyl radical, or a C₁ to C₁₀ hydrocarbyl radical, subjectto the proviso that R¹⁹ is not a carbazole or a substituted carbazoleradical. In an embodiment, one or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹is a methyl radical, a bromine, an adamantyl radical, or a combinationthereof.

In an embodiment, M is Zr; X¹ and X² are benzyl; R¹ and R¹⁴ are methyl;R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ and R²¹ are hydrogen; R¹⁷ and R¹⁹ arebromine; and Y is —CH₂CH₂—.

In an embodiment, M is Zr; X¹ and X² are benzyl; R¹, R¹⁴ and R¹⁷ aremethyl; R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ and R²¹ are hydrogen; R¹⁹ is1-adamantyl; and Y is —CH₂CH₂—.

In an embodiment, M is Hf; X¹ and X² are benzyl; R¹ and R¹⁴ are methyl;R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ and R²¹ are hydrogen; R¹⁷ is methyl;R¹⁹ is 1-adamantyl; and Y is —CH₂CH₂—.

In an embodiment, two or more different catalyst compounds are presentin the catalyst system used herein. In an embodiment, two or moredifferent catalyst compounds are present in the reaction zone where theprocess(es) described herein occur. When two transition metal compoundbased catalysts are used in one reactor as a mixed catalyst system, thetwo transition metal compounds are chosen such that the two arecompatible. Compatible catalysts are those catalysts having similarkinetics of termination and insertion of monomer and comonomer(s) and/ordo not detrimentally interact with each other. For purposes herein, theterm “incompatible catalysts” refers to and means catalysts that satisfyone or more of the following:

-   -   1) those catalysts that when present together reduce the        activity of at least one of the catalysts by greater than 50%;    -   2) those catalysts that under the same reactive conditions        produce polymers such that one of the polymers has a molecular        weight that is more than twice the molecular weight of the other        polymer; and    -   3) those catalysts that differ in comonomer incorporation or        reactivity ratio under the same conditions by more than about        30%. A simple screening method such as by ¹H or ¹³C NMR, known        to those of ordinary skill in the art, can be used to determine        which transition metal compounds are compatible. In an        embodiment, the catalyst systems use the same activator for the        catalyst compounds. In an embodiment, two or more different        activators, such as a non-coordinating anion activator and an        alumoxane, can be used in combination. If one or more catalyst        compounds contain an X¹ or X² ligand which is not a hydride, or        a hydrocarbyl, then in an embodiment the alumoxane is contacted        with the catalyst compounds prior to addition of the        non-coordinating anion activator.

In an embodiment, when two transition metal compounds (pre-catalysts)are utilized, they may be used in any ratio. In an embodiment, a molarratio of a first transition metal compound (A) to a second transitionmetal compound (B) will fall within the range of (A:B) 1:1000 to 1000:1,or 1:100 to 500:1, or 1:10 to 200:1, or 1:1 to 100:1, or 1:1 to 75:1, or5:1 to 50:1. The particular ratio chosen will depend on the exactpre-catalysts chosen, the method of activation, and the end productdesired. In an embodiment, when using two pre-catalysts, where both areactivated with the same activator, useful mole percents, based upon thetotal moles of the pre-catalysts, are 10:90 to 0.1:99, or 25:75 to 99:1,or 50:50 to 99.5:0.5, or 50:50 to 99:1, or 75:25 to 99:1, or 90:10 to99:1.

Methods to Prepare the Catalyst Compounds

In embodiments the symmetric transition metal compounds may be preparedby two general synthetic routes. The parent salan ligands are preparedby a one-step Mannich reaction from the parent phenol (Reaction A) or bya two-step imine-condensation/alkylation procedure if thesalicylaldehyde is used (Reaction B). The ligand is then converted intothe metal dibenzyl catalyst precursor by reaction with the metaltetra-aryl starting material, e.g., tetrabenzyl, to yield the finishedcomplex (Reaction C).

Asymmetric transition metal compounds may be prepared by a step-wisesynthetic route. The parent salan ligands are prepared by reaction ofthe salicylaldehyde with the diamine, followed by reduction with NaBH4.The asymmetric ligand is then formed by an HBr elimination reaction witha bromomethylphenol (Reaction D). The ligand is then converted into themetal dibenzyl catalyst precursor by reaction with the metal tetrabenzylstarting material to yield the finished complex (Reaction E).

Activators

The terms “cocatalyst” and “activator” are used interchangeably todescribe activators and are defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral catalyst compound to a catalytically active catalystcompound cation. Non-limiting activators, for example, includealumoxanes, aluminum alkyls, ionizing activators, which may be neutralor ionic, and conventional-type cocatalysts. Activators may includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl radical. Examplesof alumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the catalyst precursor compound comprises anabstractable ligand which is an alkyl, halide, alkoxide or amide.Mixtures of different alumoxanes and modified alumoxanes may also beused. In an embodiment, visually clear methylalumoxane may be used. Acloudy or gelled alumoxane can be filtered to produce a clear solutionor clear alumoxane can be decanted from the cloudy solution. A usefulalumoxane is a modified methyl alumoxane (MMAO) described in U.S. Pat.No. 5,041,584 and/or commercially available from Akzo Chemicals, Inc.under the trade designation Modified Methylalumoxane type 3A. Solidalumoxanes may also be used.

When the activator is an alumoxane (modified or unmodified), in anembodiment, the maximum amount of activator is a 5000-fold molar excessAl/M over the catalyst compound (per metal catalytic site). In anembodiment, the minimum activator-to-catalyst-compound, which isdetermined according to molar concentration of the transition metal M,in an embodiments is 1 mole aluminum or less to mole of transition metalM. In an embodiment, the activator comprises alumoxane and the alumoxaneis present at a ratio of 1 mole aluminum or more to mole of catalystcompound. In an embodiment, the minimum activator-to-catalyst-compoundmolar ratio is a 1:1 molar ratio. Other embodiments of Al:M rangesinclude from 1:1 to 500:1, or from 1:1 to 200:1, or from 1:1 to 100:1,or from 1:1 to 50:1.

In an embodiment, little or no alumoxane (i.e., less than 0.001 wt %) isused in the polymerization processes described herein. In an embodiment,alumoxane is present at 0.00 mole %, or the alumoxane is present at amolar ratio of aluminum to catalyst compound transition metal less than500:1, or less than 300:1, or less than 100:1, or less than 1:1.

The term “non-coordinating anion” (NCA) refers to an anion which eitherdoes not coordinate to a cation, or which is only weakly coordinated toa cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with this invention are those that arecompatible with the polymerization or catalyst system, stabilize thetransition metal cation in the sense of balancing its ionic charge at+¹, and yet are sufficiently labile to permit displacement duringpolymerization.

In an embodiment, an ionizing or stoichiometric activator may be used,which may be neutral or ionic, such as tri(n-butyl) ammonium boronmetalloid precursor, polyhalogenated heteroborane anions (WO 98/43983),boric acid (U.S. Pat. No. 5,942,459), or a combination thereof. In anembodiment, neutral or ionic activators alone or in combination withalumoxane or modified alumoxane activators may be used.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium, and indium, or mixtures thereof.The three substituent groups or radicals can be the same or differentand in an embodiment are each independently selected from substituted orunsubstituted alkyls, alkenyls, alkyns, aryls, alkoxy, and halogens. Inan embodiment, the three groups are independently selected from halogen,mono or multicyclic (including halosubstituted) aryls, alkyls, andalkenyl compounds, and mixtures thereof; or independently selected fromalkenyl radicals having 1 to 20 carbon atoms, alkyl radicals having 1 to20 carbon atoms, alkoxy radicals having 1 to 20 carbon atoms and aryl orsubstituted aryl radicals having 3 to 20 carbon atoms. In an embodiment,the three substituent groups are alkyl radicals having 1 to 20 carbonatoms, phenyl, naphthyl, or mixtures thereof. In an embodiment, thethree groups are halogenated aryl groups, e.g., fluorinated aryl groups.In an embodiment the neutral stoichiometric activator is trisperfluorophenyl boron or tris perfluoronaphthyl boron.

In an embodiment, ionic stoichiometric activator compounds may includean active proton, or some other cation associated with, but notcoordinated to, or only loosely coordinated to the remaining ion of theionizing compound. Suitable examples include compounds and the likedescribed in European publications EP 0 570 982 A; EP 0 520 732 A; EP 0495 375 A; EP 0 500 944 B1; EP 0 277 003 A; EP 0 277 004 A; U.S. Pat.Nos. 5,153,157; 5,198,401; 5,066,741; 5,206,197; 5,241,025; 5,384,299;5,502,124; and WO 1996/04319; all of which are herein fully incorporatedby reference.

In an embodiment compounds useful as an activator comprise a cation,which is, for example, a Bronsted acid capable of donating a proton, anda compatible non-coordinating anion which anion is relatively large(bulky), capable of stabilizing the active catalyst species (the Group 4cation, e.g.) which is formed when the two compounds are combined andsaid anion will be sufficiently labile to be displaced by olefinic,diolefinic or acetylenically unsaturated substrates or other neutralLewis bases, such as ethers, amines, and the like. Two classes of usefulcompatible non-coordinating anions are disclosed in EP 0 277,003 A1, andEP 0 277,004 A1, which include anionic coordination complexes comprisinga plurality of lipophilic radicals covalently coordinated to andshielding a central charge-bearing metal or metalloid core; and anionscomprising a plurality of boron atoms such as carboranes,metallacarboranes, and boranes.

In an embodiment, the stoichiometric activators include a cation and ananion component, and may be represented by the following formula (1):

(Z)_(d) ⁺(A^(d−))  (1)

wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base;H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinatinganion having the charge d−; and d is an integer from 1 to 3.

When Z is (L-H) such that the cation component is (L-H)_(d) ⁺, thecation component may include Bronsted acids such as protonated Lewisbases capable of protonating a moiety, such as an alkyl or aryl, fromthe catalyst precursor, resulting in a cationic transition metalspecies, or the activating cation (L-H)_(d) ⁺ is a Bronsted acid,capable of donating a proton to the catalyst precursor resulting in atransition metal cation, including ammoniums, oxoniums, phosphoniums,silyliums, and mixtures thereof, or ammoniums of methylamine, aniline,dimethylamine, diethylamine, N-methylaniline, diphenylamine,trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine,pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline,phosphoniums from triethylphosphine, triphenylphosphine, anddiphenylphosphine, oxoniums from ethers, such as dimethyl ether diethylether, tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid it may be represented by the formula:(Ar₃ C⁺), where Ar is aryl or aryl substituted with a heteroatom, or aC₁ to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented bythe formula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, and/or a C₁ to C₄₀ hydrocarbyl. In an embodiment, thereducible Lewis acid is triphenyl carbenium.

Embodiments of the anion component A^(d−) include those having theformula [M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5or 6, or 3, 4, 5 or 6; n−k=d; M is an element selected from Group 13 ofthe Periodic Table of the Elements, or boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl radicals, said Q having up to 20 carbonatoms with the proviso that in not more than one occurrence is Q ahalide, and two Q groups may form a ring structure. Each Q may be afluorinated hydrocarbyl radical having 1 to 20 carbon atoms, or each Qis a fluorinated aryl radical, or each Q is a pentafluoryl aryl radical.Examples of suitable A^(d−) components also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

In an embodiment, this invention relates to a method to polymerizeolefins comprising contacting olefins (e.g., ethylene) with a Salancatalyst compound, a chain transfer agent (CTA) and a boron containingNCA activator represented by the formula (1) where: Z is (L-H) or areducible Lewis acid; L is an neutral Lewis base (as further describedabove); H is hydrogen; (L-H) is a Bronsted acid (as further describedabove); A^(d−) is a boron containing non-coordinating anion having thecharge d− (as further described above); d is 1, 2, or 3.

In an embodiment in any of the NCA's represented by Formula 1 describedabove, the anion component A^(d−) is represented by the formula[M*k*+Q*n*]^(d*−) wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or 6(or 1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* is independentlyselected from hydride, bridged or unbridged dialkylamido, halogen,alkoxide, aryloxide, hydrocarbyl radicals, said Q* having up to 20carbon atoms with the proviso that in not more than 1 occurrence is Q* ahalogen.

This invention also relates to a method to polymerize olefins comprisingcontacting olefins (such as ethylene) with a Salan catalyst compound asdescribed above, optionally with a CTA and an NCA activator representedby the Formula (2):

R_(n)M**(ArNHal)_(4-n)  (2)

where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 2also comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, or the cation is Z_(d) ⁺ as described above.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, R is selected from the group consisting of C₁to C₃₀ hydrocarbyl radicals. In an embodiment, C₁ to C₃₀ hydrocarbylradicals may be substituted with one or more C₁ to C₂₀ hydrocarbylradicals, halide, hydrocarbyl substituted organometalloid, dialkylamido,alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C₄ to C₂₀ hydrocarbyl radicals; —SR¹, —NR² ₂, and —PR³₂, where each R¹, R², or R³ is independently a C₁ to C₃₀ hydrocarbyl asdefined above; or a C₁ to C₃₀ hydrocarbyl substituted organometalloid.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA also comprises cation comprising areducible Lewis acid represented by the formula: (Ar₃C⁺), where Ar isaryl or aryl substituted with a heteroatom, and/or a C₁ to C₄₀hydrocarbyl, or the reducible Lewis acid represented by the formula:(Ph₃C⁺), where Ph is phenyl or phenyl substituted with one or moreheteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA may also comprise a cationrepresented by the formula, (L-H)_(d) ⁺, wherein L is an neutral Lewisbase; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or(L-H)_(d) ⁺ is a Bronsted acid selected from ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. Nos. 7,297,653 and 7,799,879, which are fully incorporated byreference herein.

In an embodiment, an activator useful herein comprises a salt of acationic oxidizing agent and a noncoordinating, compatible anionrepresented by the Formula (3):

(OX^(e+))_(d)(A^(d−))_(e)  (3)

wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Suitable embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

In an embodiment, the Salan catalyst compounds, CTA's, and/or NCA'sdescribed herein can be used with bulky activators. A “bulky activator”as used herein refers to anionic activators represented by the formula:

-   where each R₁ is, independently, a halide, or a fluoride;-   each R₂ is, independently, a halide, a C₆ to C₂₀ substituted    aromatic hydrocarbyl radical or a siloxy group of the formula    —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl or    hydrocarbylsilyl radical (or R₂ is a fluoride or a perfluorinated    phenyl radical);-   each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl    radical or a siloxy group of the formula —O—Si—R_(a), where R_(a) is    a C₁ to C₂₀ hydrocarbyl radical or hydrocarbylsilyl group (or R₃ is    a fluoride or a C₆ perfluorinated aromatic hydrocarbyl radical);    wherein R₂ and R₃ can form one or more saturated or unsaturated,    substituted or unsubstituted rings (or R₂ and R₃ form a    perfluorinated phenyl ring);-   L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or    3;-   wherein the anion has a molecular weight of greater than 1020 g/mol;    and-   wherein at least three of the substituents on the B atom each have a    molecular volume of greater than 250 cubic Å, or greater than 300    cubic Å, or greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3Vs, where Vs is the scaledvolume. Vs is the sum of the relative volumes of the constituent atoms,and is calculated from the molecular formula of the substituent usingthe following table of relative volumes. For fused rings, the Vs isdecreased by 7.5% per fused ring.

Relative Element Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

Molecular Formula of MV Total each Per subst. MV Activator Structure ofboron substituents substituent (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoronaphthyl)borate

C₁₀F₇ 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl)borate

C₁₂F₉ 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 515 2060

Exemplary bulky activators useful in catalyst systems herein include:trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, and[4-tert-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], and the types disclosed in U.S.Pat. No. 7,297,653, which is fully incorporated by reference herein.

Illustrative, but not limiting, examples of boron compounds which may beused as an activator in the processes according to the instantdisclosure include: trimethylammonium tetraphenylborate,triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(tert-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, anddialkyl ammonium salts, such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and additional tri-substitutedphosphonium salts, such as tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Suitable activators include: N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph₃C⁺][B(C₆F₅)⁴⁻],[Me₃NH⁺][B(C₆F₅)⁴⁻];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate, and4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In an embodiment, the activator comprises a triaryl carbonium (such astriphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In an embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, (where alkyl ismethyl, ethyl, propyl, n-butyl, sec-butyl, or tert-butyl).

In an embodiment, any of the activators described herein may be mixedtogether before or after combination with the catalyst compound and/orCTA and/or NCA, or before being mixed with the catalyst compound and/orCTA, and/or NCA.

In an embodiment two NCA activators may be used in the polymerizationand the molar ratio of the first NCA activator to the second NCAactivator can be any ratio. In an embodiment, the molar ratio of thefirst NCA activator to the second NCA activator is 0.01:1 to 10,000:1,or 0.1:1 to 1000:1, or 1:1 to 100:1.

In an embodiment, the NCA activator-to-catalyst ratio is a 1:1 molarratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1 or 1:1 to1000:1. In an embodiment, the NCA activator-to-catalyst ratio is 0.5:1to 10:1, or 1:1 to 5:1.

In an embodiment, the catalyst compounds can be combined withcombinations of alumoxanes and NCA's (see for example, U.S. Pat. No.5,153,157, U.S. Pat. No. 5,453,410, EP 0 573 120 B1, WO 94/07928, and WO95/14044 which discuss the use of an alumoxane in combination with anionizing activator, all of which are incorporated by reference herein).

Scavengers or Co-Activators

In an embodiment the catalyst system may further include scavengersand/or co-activators. Suitable aluminum alkyl or organoaluminumcompounds which may be utilized as scavengers or co-activators include,for example, trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum and the like. Other oxophilicspecies such as diethyl zinc may be used. In an embodiment, thescavengers and/or co-activators are present at less than 14 wt %, orfrom 0.1 to 10 wt %, or from 0.5 to 7 wt %, by weight of the catalystsystem.

Catalyst Supports

In an embodiment, the catalyst system may comprise an inert supportmaterial. In an embodiment, the support material comprises a poroussupport material, for example, talc, and/or inorganic oxides. Othersuitable support materials include zeolites, clays, organoclays, or anyother organic or inorganic support material and the like, or mixturesthereof.

In an embodiment, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in catalystsystems herein include Groups 2, 4, 13, and 14 metal oxides, such assilica, alumina, and mixtures thereof. Other inorganic oxides that maybe employed either alone or in combination with the silica, and/oralumina include magnesia, titania, zirconia, montmorillonite,phyllosilicate, and/or the like. Other suitable support materialsinclude finely divided functionalized polyolefins, such as finelydivided polyethylene.

In an embodiment, the support material may have a surface area in therange of from about 10 to about 700 m2/g, pore volume in the range offrom about 0.1 to about 4.0 cc/g and average particle size in the rangeof from about 5 to about 500 μm, or the surface area of the supportmaterial is in the range of from about 50 to about 500 m²/g, pore volumeof from about 0.5 to about 3.5 cc/g and average particle size of fromabout 10 to about 200 μm. In an embodiment, a majority portion of thesurface area of the support material is in the range is from about 100to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g andaverage particle size is from about 5 to about 100 μm. In an embodiment,the average pore size of the support material is in the range of from 10to 1000 Å, or 50 to about 500 Å, or 75 to about 350 Å. In an embodiment,the support material is a high surface area, amorphous silica having asurface area greater than or equal to about 300 m²/gm, and/or a porevolume of 1.65 cm³/gm. Suitable silicas are marketed under thetradenames of Davison 952 or Davison 955 by the Davison ChemicalDivision of W.R. Grace and Company. In an embodiment the support maycomprise Davison 948.

In an embodiment, the support material should be essentially dry, thatis, essentially free of absorbed water. Drying of the support materialcan be effected by heating or calcining at about 100° C. to about 1000°C., or at a temperature of at least about 400° C., or 500° C., or 600°C. When the support material is silica, it is heated to at least 200°C., or about 200° C. to about 850° C., or at least 600° C. for a time ofabout 1 minute to about 100 hours, or from about 12 hours to about 72hours, or from about 24 hours to about 60 hours. In an embodiment, thecalcined support material must have at least some reactive hydroxyl (OH)groups to produce supported catalyst systems according to the instantdisclosure.

In an embodiment, the calcined support material is contacted with atleast one polymerization catalyst comprising at least one catalystcompound and an activator. In an embodiment, the support material,having reactive surface groups, typically hydroxyl groups, is slurriedin a non-polar solvent and the resulting slurry is contacted with asolution of a catalyst compound and an activator. In an embodiment, theslurry of the support material is first contacted with the activator fora period of time in the range of from about 0.5 hours to about 24 hours,or from about 2 hours to about 16 hours, or from about 4 hours to about8 hours. The solution of the catalyst compound is then contacted withthe isolated support/activator. In an embodiment, the supported catalystsystem is generated in situ. In an alternate embodiment, the slurry ofthe support material is first contacted with the catalyst compound for aperiod of time in the range of from about 0.5 hours to about 24 hours,or from about 2 hours to about 16 hours, or from about 4 hours to about8 hours. The slurry of the supported catalyst compound is then contactedwith the activator solution.

In an embodiment, the mixture of the catatlyst, activator and support isheated to about 0° C. to about 70° C., or to about 23° C. to about 60°C., or to room temperature. Contact times typically range from about 0.5hours to about 24 hours, or from about 2 hours to about 16 hours, orfrom about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator and the catalyst compound are at leastpartially soluble and which are liquid at reaction temperatures.Suitable non-polar solvents include alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

Polymerization Processes

In an embodiment, a polymerization processes includes contactingmonomers (such as ethylene and propylene), and optionally comonomers,with a catalyst system comprising an activator and at least one catalystcompound, as described above. In an embodiment, the catalyst compoundand activator may be combined in any order, and may be combined prior tocontacting with the monomer. In an embodiment, the catalyst compoundand/or the activator are combined after contacting with the monomer.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, or C₂ to C₂₀ alpha olefins, or C₂ to C₁₂ alpha olefins,or ethylene, propylene, butene, pentene, hexene, heptene, octene,nonene, decene, undecene, dodecene and isomers thereof. In an embodimentof the invention, the monomer comprises propylene and an optionalcomonomers comprising one or more ethylene or C₄ to C₄₀ olefins, or C₄to C₂₀ olefins, or C₆ to C₁₂ olefins. The C₄ to C₄₀ olefin monomers maybe linear, branched, or cyclic. The C₄ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups. In anembodiment, the monomer comprises ethylene or ethylene and a comonomercomprising one or more C₃ to C₄₀ olefins, or C₄ to C₂₀ olefins, or C₆ toC₁₂ olefins. The C₃ to C₄₀ olefin monomers may be linear, branched, orcyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained,monocyclic or polycyclic, and may optionally include heteroatoms and/orone or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbomadiene, dicyclopentadiene,cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene,7-oxanorbomene, 7-oxanorbomadiene, substituted derivatives thereof, andisomers thereof, or hexene, heptene, octene, nonene, decene, dodecene,cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,dicyclopentadiene, norbornene, norbomadiene, and their respectivehomologs and derivatives, or norbornene, norbomadiene, anddicyclopentadiene.

In an embodiment one or more dienes are present in the polymer producedherein at up to 10 weight %, or at 0.00001 to 1.0 weight %, or 0.002 to0.5 weight %, or 0.003 to 0.2 weight %, based upon the total weight ofthe composition. In an embodiment 500 ppm or less of diene is added tothe polymerization, or 400 ppm or less, or 300 ppm or less. In anembodiment at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Diolefin monomers useful in this invention include any hydrocarbonstructure, or C₄ to C₃₀, having at least two unsaturated bonds, whereinat least two of the unsaturated bonds are readily incorporated into apolymer by either a stereospecific or a non-stereospecific catalyst(s).In an embodiment, the diolefin monomers may be selected from alpha,omega-diene monomers (i.e. di-vinyl monomers). Moreover, the diolefinmonomers are linear di-vinyl monomers, most or those containing from 4to 30 carbon atoms. Examples of dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, 1,6-heptadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene,1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weightpolybutadienes (Mw less than 1000 g/mol). Cyclic dienes includecyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbornene,divinylbenzene, dicyclopentadiene or higher ring containing diolefinswith or without substituents at various ring positions.

In an embodiment, where butene is the comonomer, the butene source maybe a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example, C₄ raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

Polymerization processes according to the instant disclosure may becarried out in any manner known in the art. Any suspension, homogeneous,bulk, solution, slurry, or gas phase polymerization process known in theart can be used. Such processes can be run in a batch, semi-batch, orcontinuous mode. Homogeneous polymerization processes and slurryprocesses are suitable for use herein, wherein a homogeneouspolymerization process is defined to be a process where at least 90 wt %of the product is soluble in the reaction media. A bulk homogeneousprocess is suitable for use herein, wherein a bulk process is defined tobe a process where monomer concentration in all feeds to the reactor is70 volume % or more. In an embodiment, no solvent or diluent is presentor added in the reaction medium, (except for the small amounts used asthe carrier for the catalyst system or other additives, or amountstypically found with the monomer; e.g., propane in propylene). In anembodiment, the process is a slurry process. As used herein the term“slurry polymerization process” means a polymerization process where asupported catalyst is employed and monomers are polymerized on thesupported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C4-10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene,and xylene. Suitable solvents also include liquid olefins which may actas monomers or comonomers including ethylene, propylene, 1-butene,1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene,1-decene, and mixtures thereof. In an embodiment, aliphatic hydrocarbonsolvents are used as the solvent, such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof. In an embodiment, the solvent is not aromatic, or aromatics arepresent in the solvent at less than 1 wt %, or less than 0.5 wt %, orless than 0.0 wt % based upon the weight of the solvents.

In an embodiment, the feed concentration of the monomers and comonomersfor the polymerization is 60 vol % solvent or less, or 40 vol % or less,or 20 vol % or less, based on the total volume of the feedstream. Or thepolymerization is run in a bulk process.

Polymerizations can be run at any temperature and/or pressure suitableto obtain the desired ethylene polymers. Suitable temperatures and/orpressures include a temperature in the range of from about 0° C. toabout 300° C., or about 20° C. to about 200° C., or about 35° C. toabout 150° C., or about 50° C. to about 150° C., or from about 40° C. toabout 120° C., or from about 45° C. to about 80° C.; and at a pressurein the range of from about 0.35 MPa to about 10 MPa, or from about 0.45MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa.

In an embodiment, the run time of the reaction is from about 0.1 minutesto about 24 hours, or up to 16 hours, or in the range of from about 5 to250 minutes, or from about 10 to 120 minutes.

In an embodiment, hydrogen is present in the polymerization reactor at apartial pressure of 0.001 to 50 psig (0.007 to 345 kPa), or from 0.01 to25 psig (0.07 to 172 kPa), or 0.1 to 10 psig (0.7 to 70 kPa).

In an embodiment, the activity of the catalyst is at least 50g/mmol/hour, or 500 or more g/mmol/hour, or 5000 or more g/mmol/hr, or50,000 or more g/mmol/hr. In an alternate embodiment, the conversion ofolefin monomer is at least 10%, based upon polymer yield and the weightof the monomer entering the reaction zone, or 20% or more, or 30% ormore, or 50% or more, or 80% or more.

In an embodiment, the polymerization conditions include one or more ofthe following: 1) temperatures of 0 to 300° C. (or 25 to 150° C., or 40to 120° C., or 45 to 80° C.); 2) a pressure of atmospheric pressure to10 MPa (or 0.35 to 10 MPa, or from 0.45 to 6 MPa, or from 0.5 to 4 MPa);3) the presence of an aliphatic hydrocarbon solvent (such as isobutane,butane, pentane, isopentane, hexanes, isohexane, heptane, octane,dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, suchas cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, andmixtures thereof; or where aromatics are or present in the solvent atless than 1 wt %, or less than 0.5 wt %, or at 0 wt % based upon theweight of the solvents); 4) wherein the catalyst system used in thepolymerization comprises less than 0.5 mol %, or 0 mol % alumoxane, orthe alumoxane is present at a molar ratio of aluminum to transitionmetal less than 500:1, or less than 300:1, or less than 100:1, or lessthan 1:1; 5) the polymerization or occurs in one reaction zone; 6) theproductivity of the catalyst compound is at least 80,000 g/mmol/hr (orat least 150,000 g/mmol/hr, or at least 200,000 g/mmol/hr, or at least250,000 g/mmol/hr, or at least 300,000 g/mmol/hr); 7) scavengers (suchas trialkyl aluminum compounds) are absent (e.g., present at zero mol %)or the scavenger is present at a molar ratio of scavenger to transitionmetal of less than 100:1, or less than 50:1, or less than 15:1, or lessthan 10:1; and/or 8) optionally hydrogen is present in thepolymerization reactor at a partial pressure of 0.007 to 345 kPa (0.001to 50 psig) (or from 0.07 to 172 kPa (0.01 to 25 psig), or 0.7 to 70 kPa(0.1 to 10 psig)).

In an embodiment, the catalyst system used in the polymerizationcomprises no more than one catalyst compound. A “reaction zone” alsoreferred to as a “polymerization zone” is a vessel where polymerizationtakes place, for example a batch reactor. When multiple reactors areused in either series or parallel configuration, each reactor isconsidered as a separate polymerization zone. For a multi-stagepolymerization in both a batch reactor and a continuous reactor, eachpolymerization stage is considered as a separate polymerization zone. Inan embodiment, the polymerization occurs in one reaction zone.

Polyolefin Products

The instant disclosure also relates to compositions of matter producedby the methods described herein.

In an embodiment, the process described herein produces propylenehomopolymers or propylene copolymers, such as propylene-ethylene and/orpropylene-α-olefin (or C₃ to C₂₀) copolymers (such as propylene-hexenecopolymers or propylene-octene copolymers) having a Mw/Mn of greaterthan 1 to 4 (or greater than 1 to 3).

Likewise, the process of this invention produces olefin polymers, orpolyethylene and polypropylene homopolymers and copolymers. In anembodiment, the polymers produced herein are homopolymers of ethylene orpropylene, are copolymers of ethylene or having from 0 to 25 mole % (orfrom 0.5 to 20 mole %, or from 1 to 15 mole %, or from 3 to 10 mole %)of one or more C₃ to C₂₀ olefin comonomer (or C₃ to C₁₂ alpha-olefin, orpropylene, butene, hexene, octene, decene, dodecene, or propylene,butene, hexene, octene), or are copolymers of propylene or having from 0to 25 mole % (or from 0.5 to 20 mole %, or from 1 to 15 mole %, or from3 to 10 mole %) of one or more of C₂ or C₄ to C₂₀ olefin comonomer (orethylene or C₄ to C₁₂ alpha-olefin, or ethylene, butene, hexene, octene,decene, dodecene, or ethylene, butene, hexene, octene).

In an embodiment, the monomer is ethylene and the comonomer is hexene,or from 1 to 15 mole % hexene, or 1 to 10 mole % hexene.

In an embodiment, the polymers produced herein have an Mw of 5,000 to1,000,000 g/mol (e.g., 25,000 to 750,000 g/mol, or 50,000 to 500,000g/mol), and/or an Mw/Mn of greater than 1 to 40, or 1.2 to 20, or 1.3 to10, or 1.4 to 5, or 1.5 to 4, or 1.5 to 3.

In an embodiment, the polymer produced herein has a unimodal ormultimodal molecular weight distribution as determined by Gel PermeationChromotography (GPC). By “unimodal” is meant that the GPC trace has onepeak or inflection point. By “multimodal” is meant that the GPC tracehas at least two peaks or inflection points. An inflection point is thatpoint where the second derivative of the curve changes in sign (e.g.,from negative to positive or vice versa).

Unless otherwise indicated Mw, Mn, MWD are determined by GPC asdescribed in US 2006/0173123 page 24-25, paragraphs [0334] to [0341].

In an embodiment, the polymers may be linear in character, which may bedetermined by elution fractionation, wherein non-linear polymers have aCDBI of less than 45%, whereas linear polyethylene types refer topolyethylene having a CDBI of greater than 50%, the CDBI beingdetermined as described in WO93/03093 (U.S. Pat. No. 5,206,075). In anembodiment the polymer produced herein has a composition distributionbreadth index (CDBI) of 50% or more, or 60% or more, or 70% or more.CDBI is a measure of the composition distribution of monomer within thepolymer chains and is measured by the procedure described in PCTpublication WO 93/03093, published Feb. 18, 1993, specifically columns 7and 8 as well as in Wild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20,p. 441 (1982) and U.S. Pat. No. 5,008,204, including that fractionshaving a weight average molecular weight (Mw) below 15,000 are ignoredwhen determining CDBI.

Polymers with an Mw/Mn of 4.5 or less may include a significant level oflong chain branching. The long chain branching is understood to be theresult of the incorporation of terminally unsaturated polymer chains(formed by the specific termination reaction mechanism encountered withsingle site catalysts) into other polymer chains in a manner analogousto monomer incorporation. The branches are hence believed to be linearin structure and may be present at a level where no peaks can bespecifically attributed to such long chain branches in the ¹³C NMRspectrum. In an embodiment, the polymers produced according to theinstant disclosure comprise a significant amount of long chainbranching, defined as having a ratio of long chain branching of at least7 carbons per 1000 carbon atoms as determined according to the ¹³C NMRspectrum of greater than 0.5. I an embodiment, the ratio of long chainbranching with branches having at least 7 carbons, per 1000 carbon atomsas determined according to the ¹³C NMR spectrum is greater than 1, orgreater than 1.5, or greater than 2.

In an embodiment, the polymers produced according to the instantdisclosure include a significant amount of vinyl termination, defined asa ratio of vinyl groups per molecule of greater than or equal to 0.2. Inan embodiment, the polymers according to the instant disclosure comprisea ratio of vinyl groups per molecule of greater than or equal to 0.5, or0.7, or 0.8, or 0.9, or 0.95, when determined according to thedescription provided in the J. American Chemical Soc., 114,1992, pp.1025-1032, or an equivalent thereof.

This invention relates to ethylene polymers having both vinyltermination and long chain branching, which in an embodiment areproduced by the processes and using the catatlyst disclosed herein. Inan embodiment, the process described herein produces ethylenehomopolymers or ethylene copolymers, such as ethylene-alpha-olefin(preferably C₃ to C₂₀) copolymers (such as ethylene-propylenecopolymers, ethylene-hexene copolymers or ethylene-octene copolymers)having:

-   -   a) at least 50% allyl chain ends, or least 60%, 70%, 80%, 90%,        95%, 98%, or 99%; and/or    -   b) an Mn of at least 200 g/mol, measured by 1H NMR, or 250 g/mol        to 100,000 g/mol, e.g., or 200 g/mol to 75,000 g/mol, e.g., or        200 g/mol to 60,000 g/mol, or 300 g/mol to 60,000 g/mol, or 750        g/mol to 30,000 g/mol); and/or    -   c) at least 0.5 branches having 7 or more carbon atoms per 1000        carbon atoms, or 1.0 or more, or 1.25 or more, or 1.5 or more,        or 1.75 or more, or 2.0 or more, or from 0.5 to 5.0, or from 1.0        to 4.0, or from 1.5 to 3.0; and/or    -   d) a Tm of 100° C. or more, or 110° C. or more, or 120° C. or        more; and/or    -   e) a ratio of methyl chain ends, also referred to herein as        saturated chain ends, to allyl chain ends of 1:1 to 5:1, or 1:1        to 4:1, or 1:1 to 3:1; and/or    -   f) at least 50 wt % of the polymer, which may be an ethylene        homopolymer or copolymer, has one vinyl per molecule or per        chain as determined by ¹H NMR, or at least 60 wt %, or at least        70 wt %, or at least 80 wt %, or at least 90 wt %, or at least        95 wt %; and/or essentially no diene is present, or the polymer        comprises less than or equal to about 0.01 wt % diene; and/or    -   g) the polymer comprises at least 50 mol % ethylene, or at least        60 mol %, or at least 70 mol %, or at least 75 mol %, or at        least 80 mol %, or at least 85 mol %, or at least 90 mol %, or        at least 95 mol %, or essentially 100 mol % ethylene; and/or    -   h) an Mw/Mn of greater than 1 to 4, or greater than 1 to 3.

In an embodiment, polymer produced herein has less than 1400 ppmaluminum, or less than 1200 ppm, or less than 1000 ppm, or less than 500ppm, or less than 100 ppm as determined by ICPES (Inductively CoupledPlasma Emission Spectrometry), which is described in J. W. Olesik,“Inductively Coupled Plasma-Optical Emission Spectroscopy,” in theEncyclopedia of Materials Characterization, C. R. Brundle, C. A. Evans,Jr. and S. Wilson, eds., Butterworth-Heinemann, Boston, Mass., 1992, pp.633-644, which is used herein for purposes of determining the amount ofan element in a material; and/or in an embodiment, the polymer has lessthan 1400 ppm of the Group 3, 4, 5, or 6 transition metal, or of theGroup 4 transition metal, or of Ti, Zr, and/or Hf, or less than 1200ppm, or less than 1000 ppm, or less than 500 ppm, or less than 100 ppm,as determined by ICPES as discussed above.

In an embodiment of the invention, an ethylene polymer according to theinstant disclosure has less than 1400 ppm hafnium, or less than 1200ppm, or less than 1000 ppm, or less than 500 ppm, or less than 100 ppmas determined by ICPES.

In an embodiment of the invention, an ethylene polymer according to theinstant disclosure has less than 1400 ppm zirconium, or less than 1200ppm, or less than 1000 ppm, or less than 500 ppm, or less than 100 ppmas determined by ICPES.

In an embodiment, the polymer produced herein, which may be an ethylenepolymer, has a density of greater than 0.95 g/cc, or greater than 0.955g/cc, or greater than 0.96 g/cc.

In an embodiment, the ethylene polymer produced herein has a branchingindex (g′vis) of 0.9 or less, or 0.85 or less, or 0.80 or less, whereg′vis is determined as described below.

For purposes herein, Mw, Mz number of carbon atoms, g value and g′visare determined by using a High Temperature Size Exclusion Chromatograph(either from Waters Corporation or Polymer Laboratories), equipped withthree in-line detectors, a differential refractive index detector (DRI),a light scattering (LS) detector, and a viscometer. Experimentaldetails, including detector calibration, are described in: T. Sun, P.Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34,Number 19, 6812-6820, (2001) and references therein. Three PolymerLaboratories PLgel 10 mm Mixed-α LS columns are used. The nominal flowrate is 0.5 cm3/min, and the nominal injection volume is 300 L. Thevarious transfer lines, columns and differential refractometer (the DRIdetector) are contained in an oven maintained at 145° C. Solvent for theexperiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the SizeExclusion Chromatograph. Polymer solutions are prepared by placing drypolymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous agitation for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.324 g/ml at 14 5° C. The injectionconcentration is from 0.75 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples.

Prior to running each sample the DRI detector and the injector arepurged. Flow rate in the apparatus is then increased to 0.5 ml/minute,and the DRI is allowed to stabilize for 8 to 9 hours before injectingthe first sample. The LS laser is turned on 1 to 1.5 hours beforerunning the samples. The concentration, c, at each point in thechromatogram is calculated from the baseline-subtracted DRI signal,IDRI, using the following equation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymers,0.098 for butene polymers and 0.1 otherwise. Units on parametersthroughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature mini-DAWN. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, Light Scattering from Polymer Solutions, Academic Press,1971):

$\frac{K_{o}c}{\Delta \; {R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient [for purposes of thisinvention, A₂=0.0006 for propylene polymers, 0.0015 for butene polymersand 0.001 otherwise], (dn/dc)=0.104 for propylene polymers, 0.098 forbutene polymers and 0.1 otherwise, P(O) is the form factor for amonodisperse random coil, and K_(o) is the optical constant for thesystem:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( \frac{n}{c} \right)}^{2}}{\lambda^{4}N_{A}}$

where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=690 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure.

The specific viscosity, ηs, for the solution flowing through theviscometer is calculated from their outputs. The intrinsic viscosity,[η], at each point in the chromatogram is calculated from the followingequation:

η_(s) =c[η]+0.3(c[η])²

where c is concentration and was determined from the DRI output.

The branching index (g′vis) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]avg, of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromotographic slices, i, between theintegration limits.

The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(v) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis.

The parameter “g” also called a “g value” is defined to be Rg² _(pm)/Rg²_(ls), where Rg_(pm) is the radius of gyration for the polymacromer, Rg²_(ls) is the radius of gyration for the linear standard, andRg_(ls)=K_(s)M^(0.58) where K_(s) is the power law coefficient (0.023for linear polyethylene, 0.0171 for linear polypropylene, and 0.0145 forlinear polybutene), and M is the molecular weight as described above,Rg_(pm)=K_(T)M^(αs). α_(s) is the size coefficient for the polymacromer,K_(T) is the power law coefficient for the polymacromer. SeeMacromolecules, 2001, 34, 6812-6820, for guidance on selecting a linearstandards having the molecular weight and comonomer content, anddetermining K coefficients and a exponents.

¹³C NMR data was collected at 120° C. in a 10 mm probe using a Varianspectrometer with a ¹Hydrogen frequency of at least 400 MHz. A 90 degreepulse, an acquisition time adjusted to give a digital resolution between0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating was employed during the entire acquisitionperiod. The spectra were acquired using time averaging to provide asignal to noise level adequate to measure the signals of interest.Samples were dissolved in tetrachloroethane-d₂ at concentrations between10 to 15 wt % prior to being inserted into the spectrometer magnet.Prior to data analysis spectra were referenced by setting the chemicalshift of the (—CH₂—)_(n) signal where n>6 to 29.9 ppm. Chain ends forquantization were identified using the signals shown in the table below.N-butyl and n-propyl were not reported due to their low abundance (lessthan 5%) relative to the chain ends shown in the table below.

Chain End ¹³CNMR Chemical Shift P~i—Bu 23-5 to 25.5 and 25.8 to 26.3 ppmE~i—Bu 39.5 to 40.2 ppm P~Vinyl 41.5 to 43 ppm E~Vinyl 33.9 to 34.4 ppm

Samples are dissolved in d₂-1,1,2,2-tetrachloroethane, and spectrarecorded at 125° C. using a 100 MHz (or higher) NMR spectrometer.Polymer resonance peaks are referenced to mmmm=21.8 ppm. Calculationsinvolved in the characterization of polymers by NMR are described by F.A. Bovey in Polymer Conformation and Configuration (Academic Press, NewYork 1969) and J. Randall in Polymer Sequence Determination, 13C-NMRMethod (Academic Press, New York, 1977).

The “allyl chain end to vinylidene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylidene chain ends.

The “allyl chain end to vinylene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylene chain ends.

The term “allyl chain end” (also referred to as “allylic vinyl group” or“allylic vinyl end group”) is defined to be a polymer terminusrepresented by (CH₂═CH—CH₂-polymer) according to the following formula:

where M represents the polymer chain.

The term “vinylidene chain end” is defined to be a polymer terminusrepresented by (CH₃—C(═CH₂)—CH₂-polymer).

The term “vinylene chain end” is defined to be a disubstituted vinylenepolymer terminus represented by (alkyl-CH═CH—CH₂-polymer).

In an embodiment, the amount of allyl chain ends is determined using ¹HNMR at 120° C. using deuterated tetrachloroethane as the solvent on a500 MHz machine and in selected cases confirmed by ¹³C NMR. Literaturevalues have been reported for proton and carbon assignments where neatperdeuterated tetrachloroethane is used for proton spectra and a 50:50mixture of normal and perdeuterated tetrachloroethane is used for carbonspectra; all spectra are recorded at 100° C. on a BRUKER AM 300spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon,for vinyl terminated propylene oligomers, as in J. American ChemicalSoc., 114, 1992, pp. 1025-1032.

Vinyl terminated polymers typically also have a saturated chain end,also referred to as a methyl end. In polymerizations comprising C₄ orgreater monomers (or “higher olefin” monomers), the saturated chain endmay be a C₄ or greater (or “higher olefin”) chain end, as shown in theformula below:

where M represents the polymer chain and n is an integer selected from 4to 40. This is especially true when there is substantially no ethyleneor propylene in the polymerization. In an ethylene/(C₄ or greatermonomer) copolymerization, the polymer chain may initiate growth in anethylene monomer, thereby generating a saturated chain end which is anethyl chain end. In polymerizations where propylene is present, thepolymer chain may initiate growth in a propylene monomer, therebygenerating an isobutyl chain end. An “isobutyl chain end” is defined tobe an end or terminus of a polymer, represented as shown in the formulabelow:

where M represents the polymer chain. Isobutyl chain ends are determinedaccording to the procedure set out in WO 2009/155471.

Mn (¹H NMR) is determined according to the following NMR method. ¹H NMRdata is collected at either room temperature or 120° C. (for purposes ofthe claims, 120° C. shall be used) in a 5 mm probe using a Varianspectrometer with a ¹H frequency of 250 MHz, 400 MHz, or 500 MHz (forthe purpose of the claims, a proton frequency of 400 MHz is used). Dataare recorded using a maximum pulse width of 45° C., 8 seconds betweenpulses and signal averaging 120 transients. Spectral signals areintegrated and the number of unsaturation types per 1000 carbons arecalculated by multiplying the different groups by 1000 and dividing theresult by the total number of carbons. Mn is calculated by dividing thetotal number of unsaturated species into 14,000, and has units of g/mol.The chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Region Number of hydrogens Unsaturation Type (ppm) per structure AllylicVinyl 4.95-5.10 2 Vinylidene 4.70-4.84 2 Disubstituted Vinylene5.31-5.55 2 Trisubstituted Vinylene 5.11-5.30 1

Differential Scanning Calorimetry (DSC)

Crystallization temperature (T_(c)), melting temperature (or meltingpoint, T_(m)), glass transition temperature (T_(g)) and heat of fusion(H_(f)) are measured using Differential Scanning Calorimetry (DSC) on acommercially available instrument (e.g., TA Instruments 2920 DSC).Typically, 6 to 10 mg of molded polymer or plasticized polymer aresealed in an aluminum pan and loaded into the instrument at roomtemperature. Data are acquired by heating the sample to at least 30° C.above its melting temperature, typically 220° C. for polypropylene, at aheating rate of 10° C./min. The sample is held for at least 5 minutes atthis temperature to destroy its thermal history. Then the sample iscooled from the melt to at least 50° C. below the crystallizationtemperature, typically −100° C. for polypropylene, at a cooling rate of20° C./min. The sample is held at this temperature for at least 5minutes, and finally heated at 10° C./min to acquire additional meltingdata (second heat). The endothermic melting transition (first and secondheat) and exothermic crystallization transition are analyzed accordingto standard procedures. The melting temperatures (Tm) reported are thepeak melting temperatures from the second heat unless otherwisespecified. For polymers displaying multiple peaks, the meltingtemperature is defined to be the peak melting temperature from themelting trace associated with the largest endothermic calorimetricresponse (as opposed to the peak occurring at the highest temperature).Likewise, the crystallization temperature is defined to be the peakcrystallization temperature from the crystallization trace associatedwith the largest exothermic calorimetric response (as opposed to thepeak occurring at the highest temperature).

Areas under the DSC curve are used to determine the heat of transition(heat of fusion, H_(f), upon melting or heat of crystallization, H_(c),upon crystallization), which can be used to calculate the degree ofcrystallinity (also called the percent crystallinity). The percentcrystallinity (X %) is calculated using the formula: [area under thecurve (in J/g)/H° (in J/g)]*100, where H° is the ideal heat of fusionfor a perfect crystal of the homopolymer of the major monomer component.These values for H° are to be obtained from the Polymer Handbook, FourthEdition, published by John Wiley and Sons, New York 1999, except that avalue of 290 J/g is used for H° (polyethylene), a value of 140 J/g isused for H° (polybutene), and a value of 207 J/g is used for H°(polypropylene).

Heat of melting (Hm) is determined using the DSC procedure above exceptthat the sample is cooled to −100° C., held for 5 minutes then heated at10° C./min to 200° C. Hm is measured on the first melt, no the secondmelt. The Hm sample must have been aged at least 48 hours at roomtemperature and should not be heated to destroy thermal history.

Ethylene Content

Ethylene content in ethylene copolymers is determined by ASTM D 5017-96,except that the minimum signal-to-noise should be 10,000:1. Propylenecontent in propylene copolymers is determined by following the approachof Method 1 in Di Martino and Kelchermans, J. Appl. Polym. Sci. 56, 1781(1995), and using peak assignments from Zhang, Polymer 45, 2651 (2004)for higher olefin comonomers.

Mn, Mw, and Mz may also be measured by using a Gel PermeationChromatography (GPC) method using a High Temperature Size ExclusionChromatograph (SEC, either from Waters Corporation or PolymerLaboratories), equipped with a differential refractive index detector(DRI). Experimental details, are described in: T. Sun, P. Brant, R. R.Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp.6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B columns are used. The nominal flow rate is 0.5cm³/min and the nominal injection volume is 300 μL. The various transferlines, columns and differential refractometer (the DRI detector) arecontained in an oven maintained at 135° ° C. Solvent for the SECexperiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the SEC.Polymer solutions are prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities aremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/mL at room temperatureand 1.324 g/mL at 135° C. The injection concentration is from 1.0 to 2.0mg/mL, with lower concentrations being used for higher molecular weightsamples. Prior to running each sample the DRI detector and the injectorare purged. Flow rate in the apparatus is then increased to 0.5mL/minute, and the DRI is allowed to stabilize for 8 to 9 hours beforeinjecting the first sample. The concentration, c, at each point in thechromatogram is calculated from the baseline-subtracted DRI signal,I_(DRI), using the following equation:

c=K _(DRI) I _(DRI)/(dn/dc)

where KDRI is a constant determined by calibrating the DRI, and (dn/dc)is the refractive index increment for the system. The refractive index,n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of this inventionand the claims thereto (dn/dc)=0.104 for propylene polymers and ethylenepolymers, and 0.1 otherwise. Units of parameters used throughout thisdescription of the SEC method are: concentration is expressed in g/cm³,molecular weight is expressed in g/mol, and intrinsic viscosity isexpressed in dL/g.

Blends

In an embodiment, the polymer (or the polyethylene or polypropylene)produced herein is combined with one or more additional polymers priorto being formed into a film, molded part or other article. Other usefulpolymers include polyethylene, isotactic polypropylene, highly isotacticpolypropylene, syndiotactic polypropylene, random copolymer of propyleneand ethylene, and/or butene, and/or hexene, polybutene, ethylene vinylacetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methylacrylate, copolymers of acrylic acid, polymethylmethacrylate or anyother polymers polymerizable by a high-pressure free radical process,polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins,ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer,styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH),polymers of aromatic monomers such as polystyrene, polyesters,polyacetal, polyvinylidine fluoride, polyethylene glycols, and/orpolyisobutylene.

In an embodiment, the polymer (or the polyethylene or polypropylene) ispresent in the above blends, at from 10 to 99 wt %, based upon theweight of the polymers in the blend, or 20 to 95 wt %, or at least 30 to90 wt %, or at least 40 to 90 wt %, or at least 50 to 90 wt %, or atleast 60 to 90 wt %, or at least 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of theinvention with one or more polymers (as described above), by connectingreactors together in series to make reactor blends or by using more thanone catalyst in the same reactor to produce multiple species of polymer.The polymers can be mixed together prior to being put into the extruderor may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX1010 or IRGANOX 1076 available from Ciba-Geigy); phosphites (e.g.,IRGAFOS 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

In an embodiment, any of the foregoing polymers, such as the foregoingpolypropylenes or blends thereof, may be used in a variety of end-useapplications. Applications include, for example, mono- or multi-layerblown, extruded, and/or shrink films. These films may be formed by anynumber of well known extrusion or coextrusion techniques, such as ablown bubble film processing technique, wherein the composition can beextruded in a molten state through an annular die and then expanded toform a uni-axial or biaxial orientation melt prior to being cooled toform a tubular, blown film, which can then be axially slit and unfoldedto form a flat film. Films may be subsequently unoriented, uniaxiallyoriented, or biaxially oriented to the same or different extents. One ormore of the layers of the film may be oriented in the transverse and/orlongitudinal directions to the same or different extents. The uniaxialorientation can be accomplished using typical cold drawing or hotdrawing methods. Biaxial orientation can be accomplished using tenterframe equipment or a double bubble processes and may occur before orafter the individual layers are brought together. For example, apolyethylene layer can be extrusion coated or laminated onto an orientedpolypropylene layer or the polyethylene and polypropylene can becoextruded together into a film then oriented. Likewise, orientedpolypropylene could be laminated to oriented polyethylene or orientedpolyethylene could be coated onto polypropylene then optionally thecombination could be oriented even further. Typically the films areoriented in the machine direction (MD) at a ratio of up to 15, orbetween 5 and 7, and in the transverse direction (TD) at a ratio of upto 15, or 7 to 9. However, In an embodiment the film is oriented to thesame extent in both the MD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 μm are usually suitable.Films intended for packaging are usually from 10 to 50 μm thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

In an embodiment, one or more layers may be modified by coronatreatment, electron beam irradiation, gamma irradiation, flametreatment, or microwave. In an embodiment, one or both of the surfacelayers is modified by corona treatment.

Molded Products

The compositions described herein (or polypropylene compositions) mayalso be used to prepare molded products in any molding process,including but not limited to, injection molding, gas-assisted injectionmolding, extrusion blow molding, injection blow molding, injectionstretch blow molding, compression molding, rotational molding, foammolding, thermoforming, sheet extrusion, and profile extrusion. Themolding processes are well known to those of ordinary skill in the art.

Further, the compositions described herein (or polypropylenecompositions) may be shaped into desirable end use articles by anysuitable means known in the art. Thermoforming, vacuum forming, blowmolding, rotational molding, slush molding, transfer molding, wet lay-upor contact molding, cast molding, cold forming matched-die molding,injection molding, spray techniques, profile co-extrusion, orcombinations thereof are typically used methods.

Thermoforming is a process of forming at least one pliable plastic sheetinto a desired shape. Typically, an extrudate film of the composition ofthis invention (and any other layers or materials) is placed on ashuttle rack to hold it during heating. The shuttle rack indexes intothe oven which pre-heats the film before forming. Once the film isheated, the shuttle rack indexes back to the forming tool. The film isthen vacuumed onto the forming tool to hold it in place and the formingtool is closed. The tool stays closed to cool the film and the tool isthen opened. The shaped laminate is then removed from the tool. Thethermoforming is accomplished by vacuum, positive air pressure,plug-assisted vacuum forming, or combinations and variations of these,once the sheet of material reaches thermoforming temperatures, typicallyof from 140° C. to 185° C. or higher. A pre-stretched bubble step isused, especially on large parts, to improve material distribution.

Blow molding is another suitable forming means for use with thecompositions of this invention, which includes injection blow molding,multi-layer blow molding, extrusion blow molding, and stretch blowmolding, and is especially suitable for substantially closed or hollowobjects, such as, for example, gas tanks and other fluid containers.Blow molding is described in more detail in, for example, ConciseEncyclopedia of Polymer Science and Engineering 90-92 (Jacqueline I.Kroschwitz, ed., John Wiley & Sons 1990).

Likewise, molded articles may be fabricated by injecting molten polymerinto a mold that shapes and solidifies the molten polymer into desirablegeometry and thickness of molded articles. Sheets may be made either byextruding a substantially flat profile from a die, onto a chill roll, orby calendaring. Sheets are generally considered to have a thickness offrom 254 μm to 2540 μm (10 mils to 100 mils), although any given sheetmay be substantially thicker.

Non-Wovens and Fibers

The polyolefin compositions described above may also be used to preparenonwoven fabrics and fibers of this invention in any nonwoven fabric andfiber making process, including but not limited to, melt blowing,spunbonding, film aperturing, and staple fiber carding. A continuousfilament process may also be used. Or a spunbonding process is used. Thespunbonding process is well known in the art. Generally it involves theextrusion of fibers through a spinneret. These fibers are then drawnusing high velocity air and laid on an endless belt. A calender roll isgenerally then used to heat the web and bond the fibers to one anotheralthough other techniques may be used such as sonic bonding and adhesivebonding.

EMBODIMENTS

Accordingly, the instant disclosure relates to the followingembodiments:

A. A process comprising:

-   -   contacting one or more olefins with a catalyst system at a        temperature, a pressure, and for a period of time sufficient to        produce a polyolefin comprising        -   a) at least 50% allyl chain ends; and        -   b) an Mn of at least 200 g/mol, as determined by ¹H NMR;    -   the catalyst system comprising an activator and a catalyst        compound according to Formula I, Formula II, or a combination        thereof:

Formula I being represented by:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or X¹ and X² join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided, however, where M is trivalent then X² is        not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or two or more of        R¹ to R²⁸ may independently join together to form a C₄ to C₆₂        cyclic or polycyclic ring structure, or a combination thereof;        and    -   Y is a divalent C to C₂₀ hydrocarbyl;

Formula II being represented by:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   each X is, independently, a univalent C to C₂₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or X¹ and X² join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided, however, where M is trivalent then X² is        not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently, a        hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group        comprising elements from Group 13-17 of the periodic table of        the elements, or two or more of R¹ to R²¹ may independently join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, or a combination thereof; subject to the proviso that        R¹⁹ is not a carbazole or a substituted carbazole radical, and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

B. The process according to embodiment A, wherein two or more of R¹ toR²⁸ of Formula I, R¹ to R²¹ of Formula II, or a both, independently jointogether to form a C₄ to C₆₂ cyclic or polycyclic ring structure.

C. The process according to any one of embodiments A-B, wherein M ofFormula I, Formula II, or both is Hf, Ti, or Zr.

D. The process according to any one of embodiments A-C, wherein each Xof Formula I, Formula II, or both is, independently, a halogen or a C₁to C₇ hydrocarbyl radical.

E. The process according to any one of embodiments A-D, wherein each Xof Formula I, Formula II, or both is a benzyl radical.

F. The process according to any one of embodiments A-E, wherein each R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ of Formula (I),each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ of Formula (II), or both are,independently, hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl radical.

G. The process according to any one of embodiments A-F, wherein each R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ of Formula (I),each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ of Formula (II), or both are,independently, hydrogen, a halogen, or a C₁ to C₁₀ hydrocarbyl radical.

H. The process according to any one of embodiments A-G, wherein one ormore of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸of Formula I is a methyl radical, a fluoride, or a combination thereof.

I. The process according to any one of embodiments A-H, wherein thecatalyst compound is according to Formula I wherein,

-   -   M is Zr;    -   X¹ and X² are benzyl radicals;    -   R¹ and R¹⁴ are methyl radicals;    -   R² through R¹³ and R¹⁵ through R²⁸ are hydrogen; and    -   Y is —CH₂CH₂—.

J. The process according to any one of embodiments A-I, wherein thecatalyst compound is according to Formula I wherein,

-   -   M is Zr;    -   X¹ and X² are benzyl radicals;    -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;    -   R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ are hydrogen;        and    -   Y is —CH₂CH₂—.

K. The process according to any one of embodiments A-J, wherein, thecatalyst compound is according to Formula I wherein,

-   -   M is Zr;    -   X¹ and X² are benzyl radicals;    -   R¹ and R¹⁴ are methyl radicals;    -   R⁴ and R¹⁷ are fluoro groups;    -   R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ are hydrogen;        and    -   Y is —CH₂CH₂—.

L. The process according to any one of embodiments A-K, wherein thecatalyst compound is according to Formula I wherein,

-   -   M is Zr;    -   X¹ and X² are benzyl radicals;    -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;    -   R⁸, R¹¹, R²¹ and R²⁴ are tert-butyl radicals;    -   R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰,        R²², R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and    -   Y is —CH₂CH₂—.

M. The process according to any one of embodiments A-L, wherein thecatalyst compound is according to Formula I wherein,

-   -   M is Zr;    -   X¹ and X² are benzyl radicals;    -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;    -   R⁸, R¹¹, R²¹ and R²⁴ are mesityl radicals;    -   R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰,        R²², R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and    -   Y is —CH₂CH₂—.

N. The process according to any one of embodiments A-M, wherein one ormore of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ of Formula II is a methyl radical,a bromide, an adamantyl radical, or a combination thereof.

O. The process according to any one of embodiments A-N, wherein thecatalyst compound is according to Formula II wherein,

-   -   M is Zr;    -   X¹ and X² are benzyl radicals;    -   R¹ and R¹⁴ are methyl radicals;    -   R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ and R²¹ are hydrogen;    -   R¹⁷ and R¹⁹ are bromine; and    -   Y is —CH₂CH₂—.

P. The process according to any one of embodiments A-O, wherein thecatalyst compound is according to Formula II wherein,

-   -   M is Zr;    -   X¹ and X² are benzyl radicals;    -   R¹, R¹⁴ and R¹⁷ are methyl radicals;    -   R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰, and R²¹ are hydrogen;    -   R¹⁹ is a 1-adamantyl radical; and    -   Y is —CH₂CH₂—.

Q. The process according to any one of embodiments A-P, wherein thecatalyst compound is according to Formula II wherein,

-   -   M is Hf;    -   X¹ and X² are benzyl radicals;    -   R¹ and R¹⁴ and R¹⁷ are methyl radicals;    -   R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ and R²¹ are hydrogen;    -   R¹⁹ is a 1-adamantyl radical; and    -   Y is —CH₂CH₂—.

R. The process according to any one of embodiments A-Q, wherein Y ofFormula I, Formula II, or both is —CH₂CH₂— or 1,2-cyclohexylene.

S. The process according to any one of embodiments A-R, wherein Y ofFormula I, Formula II, or both is —CH₂CH₂CH₂—.

T. The process according to any one of embodiments A-S, wherein Y ofFormula I, Formula II, or both is a C₁-C₂₀ divalent hydrocarbyl radicalcomprising a linker backbone comprising from 1 to 18 carbon atomsbridging between nitrogen atoms N¹ and N².

U. The process according to any one of embodiments A-T, wherein Y ofFormula I, Formula II, or both is a C₁-C₂₀ divalent hydrocarbyl radicalcomprising O, S, S(O), S(O)₂, Si(R′)₂, P(R′), N(R′), or a combinationthereof, wherein each R′ is independently a C₁-C₁₈ hydrocarbyl radical.

V. The process according to any one of embodiments A-U, wherein theactivator comprises alumoxane, a non-coordinating anion activator, or acombination thereof.

W. The process according to any one of embodiments A-V, wherein theactivator comprises alumoxane and the alumoxane is present at a ratio of1 mole aluminum or more to mole of catalyst compound.

X. The process according to any one of embodiments A-W, wherein theactivator is represented by the formula:

(Z)_(d) ⁺(A^(d−))

-   -   wherein Z is (L-H), or a reducible Lewis Acid, wherein L is a        neutral Lewis base;    -   H is hydrogen;    -   (L-H)⁺ is a Bronsted acid;    -   A^(d−) is a non-coordinating anion having the charge d−; and    -   d is an integer from 1 to 3.

Y. The process according to any one of embodiments A-X, wherein theactivator is represented by the formula:

(Z)_(d) ⁺(A^(d−))

-   -   wherein A^(d−) is a non-coordinating anion having the charge d−;    -   d is an integer from 1 to 3, and    -   Z is a reducible Lewis acid represented by the formula: (Ar₃C⁺),        where Ar is aryl radical, an aryl radical substituted with a        heteroatom, an aryl radical substituted with one or more C₁ to        C₄₀ hydrocarbyl radicals, an aryl radical substituted with one        or more functional groups comprising elements from Groups 13-17        of the periodic table of the elements, or a combination thereof.

Z. The process according to any one of embodiments A-Y, wherein theactivator is selected from the group consisting of:

-   -   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,        triphenylcarbenium tetrakis(pentafluorophenyl)borate,        trimethylammonium tetrakis(perfluoronaphthyl)borate,        triethylammonium tetrakis(perfluoronaphthyl)borate,        tripropylammonium tetrakis(perfluoronaphthyl)borate,        tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,        tri(tert-butyl)ammonium tetrakis(perfluoronaphthyl)borate,        N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,        N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,        N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,        tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium        tetrakis(perfluoronaphthyl)borate, triphenylphosphonium        tetrakis(perfluoronaphthyl)borate, triethylsilylium        tetrakis(perfluoronaphthyl)borate,        benzene(diazonium)tetrakis(perfluoronaphthyl)borate,        trimethylammonium tetrakis(perfluorobiphenyl)borate,        triethylammonium tetrakis(perfluorobiphenyl)borate,        tripropylammonium tetrakis(perfluorobiphenyl)borate,        tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,        tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,        N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,        N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,        N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,        tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium        tetrakis(perfluorobiphenyl)borate, triphenylphosphonium        tetrakis(perfluorobiphenyl)borate, triethylsilylium        tetrakis(perfluorobiphenyl)borate,        benzene(diazonium)tetrakis(perfluorobiphenyl)borate,        [4-tert-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], trimethylammonium        tetraphenylborate, triethylammonium tetraphenylborate,        tripropylammonium tetraphenylborate, tri(n-butyl)ammonium        tetraphenylborate, tri(tert-butyl)ammonium tetraphenylborate,        N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium        tetraphenylborate,        N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,        tropillium tetraphenylborate, triphenylcarbenium        tetraphenylborate, triphenylphosphonium tetraphenylborate,        triethylsilylium tetraphenylborate,        benzene(diazonium)tetraphenylborate, trimethylammonium        tetrakis(pentafluorophenyl)borate, triethylammonium        tetrakis(pentafluorophenyl)borate, tripropylammonium        tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium        tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium        tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium        tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium        tetrakis(pentafluorophenyl)borate,        N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,        tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbenium        tetrakis(pentafluorophenyl)borate, triphenylphosphonium        tetrakis(pentafluorophenyl)borate, triethylsilylium        tetrakis(pentafluorophenyl)borate,        benzene(diazonium)tetrakis(pentafluorophenyl)borate,        trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        tri(n-butyl)ammonium        tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,        dimethyl(tert-butyl)ammonium        tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        N,N-dimethylanilinium        tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium        tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,        trimethylammonium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammonium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        tripropylammonium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        tri(n-butyl)ammonium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        tri(tert-butyl)ammonium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        N,N-dimethylanilinium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        N,N-diethylanilinium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        tropillium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        triphenylphosphonium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilylium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,        dicyclohexylammonium tetrakis(pentafluorophenyl)borate,        tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,        tri(2,6-dimethylphenyl)phosphonium        tetrakis(pentafluorophenyl)borate, triphenylcarbenium        tetrakis(perfluorophenyl)borate,        1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,        tetrakis(pentafluorophenyl)borate,        4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine,        triphenylcarbenium        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), and        combinations thereof.

A1. The process according to any one of embodiments A-Z, wherein thetemperature is from about 0° C. to about 300° C., the pressure is fromabout 0.35 MPa to about 10 MPa, the time is from about 0.1 minutes toabout 24 hours, or a combination thereof.

B1. The process according to any one of embodiments A-A1, wherein thetemperature is from about 50° C. to about 150° C.

C₁. The process according to any one of embodiments A-B1, wherein thepolymer comprises at least 50 mole % ethylene.

D1. The process according to any one of embodiments A-C1, wherein thepolymer comprises at least 75 mole % ethylene.

E1. The process according to any one of embodiments A-D1, wherein thepolymer comprises at least 99.9 mole % ethylene.

F1. The process according to any one of embodiments A-E1, wherein thepolymer comprises:

-   -   a) at least 0.5 branches having 7 or more carbon atoms per 1000        carbon atoms polymer;    -   b) a Tm of 100° C. or more determined by DSC;    -   c) a ratio of saturated chain ends to allyl chain ends of 1:1 to        5:1;    -   d) a ratio of vinyl groups per molecule as determined by ¹³C NMR        of at least 50%;    -   e) an Mn of at least 250 g/mol as determined by ¹H NMR; or a        combination thereof.

G1. The process according to any one of embodiments A-F1, wherein thepolymer comprises an Mn of 250 g/mol to 100,000 g/mol.

H1. The process according to any one of embodiments A-G1, wherein thepolymer comprises at least 1.0 branches having 7 or more carbon atomsper 1000 carbon atoms polymer.

I1. The process according to any one of embodiments A-H1, wherein thepolymer comprises a Tm of 110° C. or more.

J1. The process according to any one of embodiments A-I1, wherein thepolymer has less than 1400 ppm aluminum as determined by ICPES, lessthan 1400 ppm of the Group 3, 4, 5, or 6 transition metal, as determinedby ICPES, or a combination thereof.

K1. The process according to any one of embodiments A-J1, wherein thepolymer has a density of greater than 0.96 g/cc.

L1. The process according to any one of embodiments A-K1, wherein thepolymer has a branching index g′vis of 0.90 or less.

M1. The process according to any one of embodiments A-L1, wherein theone or more olefins comprise propylene.

N1. The process according to any one of embodiments A-M1, wherein thepolyolefin comprises at least 50 mole % propylene.

O1. A polyolefin polymer comprising:

-   -   a) at least 50% allyl chain ends; and    -   b) an Mn of at least 200 g/mol, as determined by ¹H NMR;    -   the polymer produced by a process comprising:    -   contacting one or more olefins with a catalyst system at a        temperature, a pressure, and for a period of time sufficient to        produce the polyolefin polymer;    -   the catalyst system comprising an activator and a catalyst        compound according to Formula I, Formula II, or a combination        thereof:

Formula I being represented by:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or X¹ and X² join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided, however, where M is trivalent then X² is        not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or two or more of        R¹ to R²⁸ may independently join together to form a C₄ to C₆₂        cyclic or polycyclic ring structure, or a combination thereof,        or a combination thereof; and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl;

Formula II being represented by:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or X¹ and X² join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided, however, where M is trivalent then X² is        not present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently, a        hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group        comprising elements from Group 13-17 of the periodic table of        the elements, or two or more of R¹ to R²¹ may independently join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, or a combination thereof; subject to the proviso that        R¹⁹ is not a carbazole or a substituted carbazole radical, and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical, and/or    -   wherein the polyolefin polymer is produced according to any one        of embodiments A-M1.

P1. The polyolefin polymer according to embodiment O1, comprising atleast 50 mole % ethylene.

Q1. The polyolefin polymer according to any one of embodiments O1-P1,comprising at least 75 mole % ethylene.

R1. The polyolefin polymer according to any one of embodiments O1-Q1,comprising at least 99.9 mole % ethylene.

S1. The polyolefin polymer according to any one of embodiments O1-R1,comprising:

-   -   a) at least 0.5 branches having 7 or more carbon atoms per 1000        carbon atoms polymer;    -   b) a Tm of 100° C. or more determined by DSC;    -   c) a ratio of saturated chain ends to allyl chain ends of 1:1 to        5:1;    -   d) a ratio of vinyl groups per molecule as determined by ¹³C NMR        of at least 50%;    -   e) an Mn of at least 250 g/mol as determined by 1H NMR; or a        combination thereof.

T1. The polyolefin polymer according to any one of embodiments O1-S1,comprising an Mn of 250 g/mol to 100,000 g/mol.

U1. The polyolefin polymer according to any one of embodiments O1-T1,comprising at least 1.0 branches having 7 or more carbon atoms per 1000carbon atoms polymer.

V1. The polyolefin polymer according to any one of embodiments O1-U1,comprising a Tm of 110° C. or more.

W1. The polyolefin polymer according to any one of embodiments O1-V1,comprising less than 1400 ppm aluminum as determined by ICPES, less than1400 ppm of the Group 3, 4, 5, or 6 transition metal, as determined byICPES, or a combination thereof.

X1. The polyolefin polymer according to any one of embodiments O1-W1,comprising a density of greater than 0.96 g/cc.

Y1. The polyolefin polymer according to any one of embodiments O1-X1,comprising a branching index g′vis of 0.90 or less.

Z1. The polyolefin polymer according to any one of embodiments O1-Y1,comprising propylene.

A2. The polyolefin polymer according to any one of embodiments O1-A2,comprising at least 50 mole % propylene.

Examples

The foregoing discussion can be further described with reference to thefollowing non-limiting examples. Four illustrative catalyst compounds(A, B, C and D), each according to one or more embodiments described,were synthesized and some were used to polymerize olefins. All reactionswere carried out under a purified nitrogen atmosphere using standardglovebox, high vacuum or Schlenk techniques, unless otherwise noted. Allsolvents used were anhydrous, de-oxygenated and purified according toknown procedures. All starting materials were either purchased fromAldrich and purified prior to use or prepared according to proceduresknown to those skilled in the art.

Synthesis of Compounds A-D

9-(2-Methoxy-5-methylphenyl)-9H-carbazole (1)

2-Bromo-4-methylanisole (20.11 g, 100 mmol, 1 equiv) and carbazole(20.06 g, 120 mmol, 1.2 equiv) were dissolved in 1,4-dioxane (400 mL).Potassium phosphate tribasic (37.15 g, 175 mmol, 1.75 equiv), copper (I)iodide (0.95 g, 5 mmol, 0.05 equiv) and racemictrans-1,2-diaminocyclohexane (2.4 mL, 20 mmol, 0.2 equiv) were added andthe reaction was refluxed for two days. The reaction was cooled to roomtemperature, then partitioned with ethyl acetate (200 mL) and water (300mL). The aqueous layer was extracted with ethyl acetate (3×200 mL). Thecombined organic layers were washed with saturated brine, dried oversodium sulfate, filtered, and concentrated under reduced pressure. Theresidue was purified over silica gel (150 g), eluting with 3% ethylacetate in heptanes to give compound 1 (13.5 g, 45% yield) as a yellowsolid.

2-(9H-Carbazol-9-yl)-4-methylphenol (2)

A 1.0 M boron tribromide solution in dichloromethane (90 mL, 90 mmol,1.9 equiv) was added dropwise at −78° C., over 30 minutes, to a solutionof compound 1 (13.5 g, 46.98 mmol, 1 equiv) in anhydrous dichloromethane(400 mL). The reaction was warmed to room temperature, when liquidchromatography-mass spectrometry (LCMS) indicated that the reaction wascomplete. The reaction was quenched with ice-water (200 mL). The layerswere separated and the aqueous phase was extracted with dichloromethane(2×100 mL). The combined organic layers were dried over sodium sulfate,filtered, and concentrated under reduced pressure. The residue waspurified on an ANALOGIX 40-150 g column, eluting with a gradient of 0 to20% ethyl acetate in heptanes to give compound 2 (12.3 g, 95% yield) asa yellow oil.

6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-4-methylphenol)(3)

A mixture of compound 2 (3.4 g, 12.44 mmol, 2 equiv), paraformaldehyde(1.87 g, 62.2 mmol, 10 equiv), N,N′-dimethylethylenediamine (0.67 mL,6.22 mmol, 1 equiv) and anhydrous ethanol (100 mL) was refluxed for 18hours. The reaction was cooled to room temperature, and thenconcentrated under reduced pressure. The residue was purified on anANALOGIX 25-60 g column, eluting with a gradient of 0 to 30% ethylacetate in heptanes to give compound 3 (1.1 g, 27% yield) as a whitesolid.

9-(5-Fluoro-2-methoxyphenyl)-9H-carbazole (4)

2-Bromo-4-fluoroanisole (20 g, 10 mmol, 1 equiv) and carbazole (18.4 g,11 mmol, 1.1 equiv) were dissolved in 1,4-dioxane (200 mL). Potassiumphosphate tribasic hydrate (46 g, 20 mmol, 2 equiv), copper(I) iodide (1g, 0.5 mmol, 0.05 equiv) and 1,2-diaminopropane (1 mL, 1.3 mmol, 0.13equiv) were added and the reaction was refluxed for 18 hours. Thereaction was cooled to room temperature and filtered through celite. Thefiltrate was concentrated under reduced pressure and the residue waspurified over silica gel (250 g), eluting with gradient of 0 to 10%ethyl acetate in heptanes to give compound 4 (7.6 g, 26% yield) as anoff white solid that was contaminated with carbazole. This material wasused subsequently.

2-(9H-Carbazol-9-yl)-4-fluorophenol (5)

A 1.0 M boron tribromide solution in dichloro-methane (60 mL, 60 mmol, 3equiv) was added dropwise over 30 minutes at −78° C. to a solution ofcompound 4 (5.8 g, 20 mmol, 1 equiv) in dichloromethane (60 mL). Thereaction was stirred at −78° C. for 4 hours, when ¹H-NMR indicated thatthe reaction was complete. The reaction was poured into saturated sodiumbicarbonate (100 mL) and the pH adjusted to 8 with 10% sodium hydroxide.The layers were separated and the aqueous phase was extracted withdichloro-methane (3×20 mL). The combined organic layers were dried oversodium sulfate, filtered, and concentrated under reduced pressure. Theresidue was purified over silica gel (100 g), eluting with a gradient of60 to 100% dichloromethane in heptanes. The product containing fractionswere combined, concentrated under reduced pressure and triturated with20% methyl tert-butyl ether in heptanes (10 mL) to give compound 5 (4.3g, 78% yield) as a white solid.

6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-4-fluorophenol)(6)

A mixture of compound 5 (1.5 g, 5.4 mmol, 2 equiv), paraformaldehyde(716 mg, 5.4 mmol, 2 equiv), N,N′-dimethylethylenediamine (300 L, 2.7mmol, 1 equiv) and anhydrous ethanol (20 mL) was refluxed for 18 hours(reaction was ˜60% complete after 2 hours). The reaction was cooled toroom temperature, then concentrated under reduced pressure. The residuewas purified over silica gel (50 g), eluting with a gradient of 60 to100% dichloromethane in heptanes to give compound 6 (640 mg, 34% yield)as a white solid.

2-(9H-carbazol-9-yl)-6-(1,3-dimethylimidazolidin-2-yl)phenol (7)

In a 100 mL round bottom flask, 2-(9H-carbazol-9-yl)salicylaldehyde(0.573 g, 2.06 mmol) was dissolved in 30 mL of methanol and heated to50° C. Ethylenediamine (0.176 g, 2.00 mmol) was also dissolved in 10 mLof methanol. When all of the 2-(9H-carbazol-9-yl)salicylaldehyde wasdissolved, the solution of ethylene diamine was slowly added. After twohours, the flask was removed from the heat source and allowed to coolovernight. A precipitate was collected and used in the next step withoutfurther purification.

2-(9H-carbazol-9-yl)-6-((methyl(2-(methylamino)ethyl)amino)methyl)phenol (8)

A slurry of 7 from the previous synthesis was stirred at roomtemperature in a 100 mL round bottom flask. Sodium borohydride (0.640 g,16.9 mmol) was added in small portions over 30 minutes. Gas evolutionwas observed. After three hours, the methanol was removed under vacuumand water was added. The resulting solids were filtered and washed withcold methanol. The white solids were dried under vacuum to yield 8(0.585 g, 79% yield).

2-(((2-((3-(9H-carbazol-9-yl)-2-hydroxybenzyl)(methyl)amino)ethyl)(methyl)-amino)methyl)-4,6-dibromophenol(9)

8 (0.218 g, 0.606 mmol) and 2-bromomethyl-4,6-dibromophenol (0.209 g,0.606 mmol) were dissolved in 20 mL of THF. Triethylamine (1.2 mL, 8.61mmol) was added to the slightly pink solution. A white precipitateformed immediately. The reaction was allowed to stir overnight afterwhich time the volatiles were removed and methanol added to make aslurry. The solids were filtered and dried under vacuum resulting in awhite solid (0.215 g, 57% yield).

[6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-4-methylphenol)]zirconium(IV)dibenzyl(A)

Under a nitrogen atmosphere, a toluene solution (5 mL) of 3 (107 mg,0.17 mmol) was added to a yellow toluene solution (5 mL) of ZrBn₄ (77mg, 0.17 mmol), forming a deep yellow solution. After stirring at roomtemperature for 15 minutes, the solvent was removed to give a yellowsticky solid. The product was washed with pentane and dried under vacuumto give compound A as a yellow solid (yield 135 mg, 88%). Compounds Bthrough D were made in a similar manner from compounds 6, 9 or 3 and thecorresponding Group IV tetrabenzyl precursors.

Polymerization Process:

Ethylene polymerizations were carried out in a parallel pressurereactor, which is described in U.S. Pat. Nos. 6,306,658, 6,455,316 and6,489,1681; WO 00/09255; and Murphy et al., J. Am. Chem. Soc., 2003,125, 4306-4317, each of which is incorporated herein by reference. Apre-weighed glass vial insert and disposable stirring paddle were fittedto each reaction vessel of the reactor, which contained 48 individualreaction vessels. The reactor was then closed and each vessel wasindividually heated to a set temperature (between 75 and 140° C.) andpressurized to a pre-determined pressure of ethylene (generally 0.93 MPa(135 psi)). Five hundred equivalents of methylalumoxane solution (30 wt% in toluene) were then added to act as a co-catalyst/scavenger. Thecontents of the vessel were then stirred at 800 rpm. A toluene solutionof catalyst (A-D, 0.20 mmol/L, 5-20 nmol) and another aliquot ofisohexane (500 uL) were then added to the reactor. All runs wereperformed in quadruplicate. While maintaining ethylene pressure in eachreaction vessel at the pre-set level by computer control, the reactionwas then allowed to proceed until a set time limit (usually 30 min) oruntil a set amount of ethylene had been taken up by the reaction. Atthis point, the reaction was quenched by exposure to air. After thepolymerization reaction, the glass vial insert containing the polymerproduct and solvent were removed from the pressure cell and the inertatmosphere glovebox, and the volatile components were removed using aGENEVAC HT-12 centrifuge and GENEVAC VC3000D vacuum evaporator operatingat elevated temperature and reduced pressure. Representative polymersamples from each catalyst under each polymerization condition werecollected and analyzed by 1H and 13C NMR spectroscopy to determineproperties such as Mn, number of ethyl branches/1000 carbons, amount oflong chain branching (LCB)/1000 carbons and number of vinyl end groupsper polymer chain.

Polymerization data shown in Table 1 are intended to be representativeof the catalytic behavior of compounds A-D and not comprehensive.

TABLE 1 Selected High Throughput Polymerization Results Temp. AmountPressure Time Yield Activity Run Cat. Activator (° C.) (nmol) (MPa(g))(sec) (mg) (g/mmol/h/b) 1 A MAO 75 10 0.931 6 179 1,154,000 2 A MAO 7510 0.931 5 191 1,479,000 3 A MAO 75 10 0.931 8 198 955,000 4 A MAO 75 100.931 8 204 984,000 5 A MAO 95 10 0.931 8 154 743,000 6 A MAO 95 100.931 9 160 689,000 7 A MAO 95 10 0.931 9 143 615,000 8 A MAO 95 100.931 8 136 655,000 9 A MAO 115 10 0.931 10 115 446,000 10 A MAO 115 100.931 11 100 352,000 11 A MAO 115 10 0.931 13 83 245,000 12 A MAO 115 100.931 16 73 176,000 13 A MAO 120 5 0.931 16 83 401,000 14 A MAO 120 50.931 14 88 485,000 15 A MAO 120 5 0.931 16 77 372,000 16 A MAO 120 50.931 13 72 429,000 17 A MAO 130 5 0.931 50 60 92,500 18 A MAO 130 50.931 43 57 102,000 19 A MAO 130 5 0.931 136 53 29,900 20 A MAO 130 50.931 122 52 32,700 21 A MAO 140 5 0.931 1800 33 1420 22 A MAO 140 50.931 1805 17 720 23 A MAO 140 5 0.931 1803 12 520 24 A MAO 140 5 0.9311803 3 130 25 B MAO 75 5 0.931 8 181 1,750,000 26 B MAO 75 5 0.931 6 1772,276,000 27 B MAO 75 5 0.931 8 168 1,625,000 28 B MAO 75 5 0.931 5 1612,493,000 29 B MAO 95 5 0.931 8 89 864,000 30 B MAO 95 5 0.931 8 89863,000 31 B MAO 95 5 0.931 8 96 932,000 32 B MAO 95 5 0.931 10 73565,000 33 B MAO 115 5 0.931 16 65 313,000 34 B MAO 115 5 0.931 484 406390 35 B MAO 115 5 0.931 21 65 240,000 36 B MAO 115 5 0.931 33 54127,000 37 B MAO 120 5 0.931 72 50 53,800 38 B MAO 120 5 0.931 70 5257,800 39 B MAO 120 5 0.931 74 52 54,700 40 B MAO 120 5 0.931 37 62130,000 41 B MAO 130 5 0.931 603 43 5550 42 B MAO 130 5 0.931 1806 401720 43 B MAO 130 5 0.931 1800 18 790 44 B MAO 130 5 0.931 1805 43 183045 B MAO 140 5 0.931 1801 13 540 46 B MAO 140 5 0.931 1802 3 120 47 BMAO 140 5 0.931 1807 8 330 48 B MAO 140 5 0.931 1803 2 90 49 C MAO 75 50.931 14 134 741,000 50 C MAO 75 5 0.931 14 140 774,000 51 C MAO 75 50.931 11 120 846,000 52 C MAO 75 5 0.931 11 129 910,000 53 C MAO 95 50.931 14 82 454,000 54 C MAO 95 5 0.931 11 79 557,000 55 C MAO 95 50.931 14 67 372,000 56 C MAO 95 5 0.931 12 85 547,000 57 C MAO 115 50.931 85 49 44,900 58 C MAO 115 5 0.931 60 47 60,700 59 C MAO 115 50.931 42 51 94,100 60 C MAO 115 5 0.931 163 40 19,200 61 C MAO 120 50.931 1804 24 1010 62 C MAO 120 5 0.931 232 46 15,500 63 C MAO 120 50.931 1802 35 1490 64 C MAO 120 5 0.931 296 45 11,700 65 C MAO 130 50.931 1807 16 680 66 C MAO 130 5 0.931 1806 12 510 67 C MAO 130 5 0.9311802 7 320 68 C MAO 130 5 0.931 1802 15 660 69 C MAO 140 5 0.931 1800 00 70 C MAO 140 5 0.931 1805 1 60 71 C MAO 140 5 0.931 1802 3 130 72 CMAO 140 5 0.931 1801 2 70 73 D MAO 75 5 0.931 28 81 223,000 74 D MAO 755 0.931 26 81 242,000 75 D MAO 75 5 0.931 26 78 231,000 76 D MAO 75 50.931 26 75 223,000 77 D MAO 95 5 0.931 30 20 51,300 78 D MAO 95 5 0.93130 66 171,000 79 D MAO 95 5 0.931 32 63 152,000 80 D MAO 95 5 0.931 3065 167,000 81 D MAO 115 5 0.931 69 51 57,000 82 D MAO 115 5 0.931 1800 00 83 D MAO 115 5 0.931 75 51 52,500 84 D MAO 115 5 0.931 1800 4 160 85 DMAO 120 5 0.931 1801 11 490 86 D MAO 120 5 0.931 1801 32 1370 87 D MAO120 5 0.931 1802 26 1130 88 D MAO 120 5 0.931 1802 30 1290 89 D MAO 1305 0.931 1803 6 280 90 D MAO 130 5 0.931 1800 3 110 91 D MAO 130 5 0.9311801 9 370 92 D MAO 130 5 0.931 1800 3 130 93 D MAO 140 5 0.931 1801 3110 94 D MAO 140 5 0.931 1801 1 60 95 D MAO 140 5 0.931 1800 2 90 96 DMAO 140 5 0.931 1802 3 130

TABLE 2 Selected Polymer Characterization Run 1 5 9 13 17 25 49 73Catalyst A A A A A B C D Temperature (° C.) 75 95 115 120 130 75 75 75Ethyl branches/1000 C. 0.5 0.4 0.4 0.3 0.5 1.2 0.7 0.2 LCB*/1000 C. 2.22.1 1.4 0.7 0.7 2.3 0.7 0.1 g′(vis) 0.775 ND ND ND ND 0.835 Mn (by ¹HNMR) 4,163 3,511 2,922 2,777 2,758 3,039 2,863 10,189 Mn (by GPC) 4,798ND ND ND ND 2,622 Density (g/cc) 0.962 ND ND ND ND 0.964 >0.970 0.966Ethyl branches/molecule 0.15 0.10 0.08 0.06 0.10 0.26 0.15 0.15LCB*/molecule 0.64 0.54 0.29 0.14 0.14 0.50 0.14 0.08 Vinylgroups/molecule 0.95 0.97 0.94 0.94 0.93 0.95 0.98 0.88 Notes: LCB* =Long Chain Branching is longer than 6 carbons and calculations assumeall LCB is “Y-type”. ND = not determined

As the data show, the catalyst compounds, catalyst systems, andpolymerization processes disclosed herein provide novel and improvedcatalyst and systems for the polymerization of olefins, which producepolymers having improved properties, such as high polymer melting point,high polymer molecular weights, an increased conversion and/or comonomerincorporation, which may further include a significant amount of longchain branching and/or a significant amount of vinyl termination.

The catalysts in an embodiment provide improvement in catalyst activity,produce polymers with improved properties or both. In an embodimentcrystallographic techniques indicate that the appended ring system orsystems (e.g., the carbazole ring systems) are oriented transversely,e.g., perpendicular, to the phenol rings. In an embodiment thesecatalysts have a structure to provide a broad corridor for the polymerylmoiety to reside and for the monomer to insert during the polymerizationprocess. As such, catalysts according to one embodiment of the instantdisclosure provide for an ability to control one or more characteristicsof polymerization, tacticity, comonomer insertion, and the like.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text, provided however that anypriority document not named in the initially filed application or filingdocuments is NOT incorporated by reference herein. As is apparent fromthe foregoing general description and the specific embodiments, whileforms of the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.Likewise whenever a composition, an element or a group of elements ispreceded with the transitional phrase “comprising”, it is understoodthat we also contemplate the same composition or group of elements withtransitional phrases “consisting essentially of,” “consisting of”,“selected from the group of consisting of,” or “is” preceding therecitation of the composition, element, or elements and vice versa.

1-21. (canceled)
 22. A polyolefin comprising: a) at least 50% allylicvinyl chain ends per polymer molecule; b) an Mn of at least 200 g/mol,as determined by ¹H NMR; and c) a ratio of long chain branching of atleast 7 carbons per 1000 carbon atoms as determined according to the ¹³CNMR spectrum of greater than 0.5.
 23. The polyolefin of claim 22,comprising at least 50 mole % ethylene.
 24. The polyolefin of claim 22,comprising: a melting point (T_(m)) of 100° C. or more determined bydifferential scanning calorimetry (DSC).
 25. The polyolefin of claim 22,comprising an Mn of at least 250 g/mol as determined by ¹H NMR.
 26. Thepolyolefin of claim 22, comprising a ratio of long chain branching of atleast 7 carbons per 1000 carbon atoms as determined according to the ¹³CNMR spectrum of greater than 1.0.
 27. The polyolefin of claim 22,comprising a melting point (T_(m)) of 110° C. or more determined bydifferential scanning calorimetry (DSC).
 28. The polyolefin of claim 22,comprising less than 1400 ppm aluminum as determined by inductivelycoupled plasma emission spectrometry (ICPES), less than 1400 ppm of aGroup 3, 4, 5, or 6 transition metal, as determined by inductivelycoupled plasma emission spectrometry (ICPES), or a combination thereof.29. The polyolefin of claim 22, comprising a density of greater than0.96 g/mL.
 30. The polyolefin claim 22, comprising a branching indexg′vis of 0.90 or less.
 31. The polyolefin of claim 22, comprisingpropylene.
 32. The polyolefin of claim 22, comprising a ratio ofsaturated chain ends to allylic vinyl chain ends of 1:1 to 5:1.
 33. Thepolyolefin of claim 22, wherein at least 80 wt % of the polyolefin hasone allylic vinyl group per molecule.
 34. The polyolefin of claim 22,comprising a weight average molecular weight (M_(w)) of 5,000 to1,000,000 g/mol.
 35. The polyolefin of claim 22, comprising an Mw/Mn ofgreater than 1 to
 4. 36. The polyolefin of claim 22, comprising at least99.9 mole percent ethylene.
 37. The polyolefin of claim 22, wherein thepolyolefin is produced by a process comprising contacting one or moreolefins with a catalyst system at a temperature, a pressure, and for aperiod of time sufficient to produce the polyolefin, wherein thecatalyst system comprises an activator and a salan catalyst precursorcompound.
 38. The polyolefin of claim 37, wherein the catalyst compoundis according to Formula I represented by:

where: M is a Group 4, 5 or 6 transition metal; each X is,independently, a univalent C₁ to C₂₀ hydrocarbyl radical, a functionalgroup comprising elements from Groups 13-17 of the periodic table of theelements, or X¹ and X² join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure provided, however, where M is trivalent thenX² is not present; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵,R²⁶, R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbylradical, a functional group comprising elements from Groups 13-17 of theperiodic table of the elements, or two or more of R¹ to R²⁸ mayindependently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure, or a combination thereof, or a combination thereof; andY is a divalent C₁ to C₂₀ hydrocarbyl.
 39. The polyolefin of claim 37,wherein the catalyst compound is according to Formula II represented by:

where: M is a Group 4, 5 or 6 transition metal; each X is,independently, a univalent C₁ to C₂₀ hydrocarbyl radical, a functionalgroup comprising elements from Groups 13-17 of the periodic table of theelements, or X¹ and X² join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure provided, however, where M is trivalent thenX² is not present; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently,a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group comprisingelements from Group 13-17 of the periodic table of the elements, or twoor more of R¹ to R²¹ may independently join together to form a C₄ to C₆₂cyclic or polycyclic ring structure, or a combination thereof; subjectto the proviso that R¹⁹ is not a carbazole or a substituted carbazoleradical, and Y is a divalent C₁ to C₂₀ hydrocarbyl radical.
 40. Apolyolefin comprising: a) a ratio of long chain branching of at least 7carbons per 1000 carbon atoms as determined according to the ¹³C NMRspectrum of greater than 0.5; b) a melting point (T_(m)) of 100° C. ormore determined by differential scanning calorimetry (DSC); c) a ratioof saturated chain ends to allylic vinyl chain ends of 1:1 to 5:1; d) aratio of allylic vinyl groups per molecule as determined by ¹³C NMR ofat least 50%; e) an Mn of at least 250 g/mol as determined by ¹H NMR;and f) at least 50 mole % ethylene.
 41. The polyolefin of claim 40,further comprising: wherein the ratio of long chain branching of atleast 7 carbons per 1000 carbon atoms as determined according to the ¹³CNMR spectrum is greater than 1; wherein the melting point (T_(m)) 100°C. or more determined by differential scanning calorimetry (DSC) is 100°C. or more; wherein at least 80 wt % of the polyolefin has one allylicvinyl group per molecule; wherein the ratio of saturated chain ends toallylic vinyl chain ends is 1:1 to 4:1; a density of greater than 0.96g/mL; a branching index g′vis of 0.90 or less; a weight averagemolecular weight (M_(w)) of 5,000 to 1,000,000 g/mol; an Mw/Mn ofgreater than 1 to 4; at least 99.9 mole percent ethylene; or acombination thereof.